U.S. patent number 10,526,446 [Application Number 15/856,721] was granted by the patent office on 2020-01-07 for polycarbonate resin composition, method for producing same, and molded object.
This patent grant is currently assigned to Mitsubishi Chemical Corporation. The grantee listed for this patent is Mitsubishi Chemical Corporation. Invention is credited to Asami Kakiuchi, Takao Kuno, Hisanori Mori, Tomohiko Tanaka.
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United States Patent |
10,526,446 |
Tanaka , et al. |
January 7, 2020 |
Polycarbonate resin composition, method for producing same, and
molded object
Abstract
The present invention aims at providing a polycarbonate resin
composition having excellent transparency and possessing high
levels of biogenic substance content rate, heat resistance, wet
heat resistance and impact resistance in a balanced manner, a
production method thereof, and a molded body of the polycarbonate
resin composition. The present invention is a polycarbonate resin
composition including a polycarbonate resin (A) containing a
constitutional unit derived from a compound represented by the
following formula (1), and an aromatic polycarbonate resin (B), a
production method thereof, and a molded body of the resin
composition: ##STR00001##
Inventors: |
Tanaka; Tomohiko (Mie,
JP), Kakiuchi; Asami (Mie, JP), Kuno;
Takao (Mie, JP), Mori; Hisanori (Mie,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsubishi Chemical Corporation |
Chiyoda-ku |
N/A |
JP |
|
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Assignee: |
Mitsubishi Chemical Corporation
(Chiyoda-ku, JP)
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Family
ID: |
57608735 |
Appl.
No.: |
15/856,721 |
Filed: |
December 28, 2017 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20180118883 A1 |
May 3, 2018 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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PCT/JP2016/069357 |
Jun 29, 2016 |
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Foreign Application Priority Data
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Jun 30, 2015 [JP] |
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2015-131491 |
Jun 30, 2015 [JP] |
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2015-131492 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L
69/00 (20130101); C08G 64/0208 (20130101); C08K
3/08 (20130101); C08G 64/302 (20130101); C08G
64/40 (20130101); C08K 5/00 (20130101); C08K
3/00 (20130101); C08G 64/16 (20130101); C08L
69/00 (20130101); C08K 3/105 (20180101); C08L
69/00 (20130101); C08L 69/00 (20130101); C08L
69/00 (20130101); C08K 2003/0818 (20130101) |
Current International
Class: |
C08G
64/16 (20060101); C08K 3/08 (20060101); C08G
64/02 (20060101); C08G 64/40 (20060101); C08K
5/00 (20060101); C08L 69/00 (20060101); C08G
64/30 (20060101); C08K 3/00 (20180101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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102597057 |
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Jul 2012 |
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CN |
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102656231 |
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Sep 2012 |
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CN |
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103370373 |
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Oct 2013 |
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CN |
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103930807 |
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Jul 2014 |
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CN |
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2 511 339 |
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Oct 2012 |
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EP |
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2 677 003 |
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Dec 2013 |
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EP |
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2009-20963 |
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Jan 2009 |
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JP |
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2009-62501 |
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Mar 2009 |
|
JP |
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2011-127108 |
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Jun 2011 |
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JP |
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2014-205829 |
|
Oct 2014 |
|
JP |
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WO 2004/111106 |
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Dec 2004 |
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WO |
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WO 2005/066239 |
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Jul 2005 |
|
WO |
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WO 2006/041190 |
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Apr 2006 |
|
WO |
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WO 2007/063823 |
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Jun 2007 |
|
WO |
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WO 2011/071162 |
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Jun 2011 |
|
WO |
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WO 2012/111721 |
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Aug 2012 |
|
WO |
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WO 2012/157766 |
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Nov 2012 |
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WO |
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WO 2013/039178 |
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Mar 2013 |
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WO |
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WO 2017/000154 |
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Jan 2017 |
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WO |
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Other References
Extended Search Report dated Dec. 14, 2018 in European Patent
Application No. 16817994.3, 6 pages. cited by applicant .
International Search Report dated Sep. 6, 2016 in
PCT/JP2016/069357, filed on Jun. 29, 2016 (with English
Translation). cited by applicant .
Combined Chinese Office Action and Search Report dated May 29, 2019
in Chinese Patent Application No. 201680038136.9 (with English
translation of Office Action and English translation of Category of
Cited Documents), 10 pages. cited by applicant.
|
Primary Examiner: Buttner; David J
Attorney, Agent or Firm: Oblon, McClelland, Maier &
Neustadt, L.L.P.
Claims
The invention claimed is:
1. A polycarbonate resin composition comprising: a melt
transesterification reaction product of a polycarbonate resin (A)
containing a constitutional unit derived from a compound
represented by formula (1), and an aromatic polycarbonate resin
(B), in the presence of at least one compound (C) selected from the
group consisting of compounds of Group I metals of the long-form
periodic table and compounds of Group II metals of the long-form
periodic table, wherein: the melt transesterification reaction is
conducted under reduced pressure, the content of the compound (C)
per 100 parts by weight of the total amount of the polycarbonate
resin (A) and the aromatic polycarbonate resin (B) is from 0.8 to
1,000 ppm by weight in terms of the metal in the compound (C), and
the glass transition temperature as measured by differential
scanning calorimetric analysis is single: ##STR00010##
2. The polycarbonate resin composition according to claim 1,
wherein a total light transmittance of a molded body of the
polycarbonate resin having a thickness of 2 mm obtained by molding
the polycarbonate resin composition is 80% or more.
3. The polycarbonate resin composition according to claim 1,
wherein the compound (C) comprises a Group I metal of the long-form
periodic table and a Group II metal of the long-form period
table.
4. The polycarbonate resin composition according to claim 1,
wherein the composition contains, as the compound (C), at least a
compound of a Group I metal of the long-form periodic table and the
content of the compound of a Group I metal of the long-form period
table per 100 parts by weight of the total amount of the
polycarbonate resin (A) and the aromatic polycarbonate resin (B) is
from 0.8 to 1,000 ppm by weight in terms of the metal.
5. The polycarbonate resin composition according to claim 1,
wherein the compound (C) is at least one member selected from the
group consisting of an inorganic salt of a carbonate, a
carboxylate, a phenolate, a halogen compound and a hydroxylated
compound.
6. The polycarbonate resin composition according to claim 1,
wherein the compound (C) is at least one member selected from the
group consisting of a sodium compound, a potassium compound and a
cesium compound.
7. The polycarbonate resin composition according to claim 1,
further comprising an acidic compound (E).
8. The polycarbonate resin composition according to claim 7,
wherein a content of the acidic compound (E) is from 0.1 to 5 times
by mol relative to the content of the metal in the compound
(C).
9. A molding body comprising the polycarbonate resin composition
according to claim 1.
10. A polycarbonate resin composition comprising: a melt
transesterification reaction product of a polycarbonate resin (A)
containing a constitutional unit derived from a compound
represented by formula (1), and an aromatic polycarbonate resin
(B), in the presence of at least one compound (C) selected from the
group consisting of compounds of Group I metals of the long-form
periodic table and compounds of Group II metals of the long-form
periodic table, and a crown ether compound (D), wherein: the melt
transesterification reaction is conducted under reduced pressure,
the content of the compound (C) per 100 parts by weight of the
total amount of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) is from 0.8 to 1,000 ppm by weight in terms
of the metal in the compound (C), and the content of the crown
ether compound (D) is from 0.1 to 10 times by mol relative the
amount in terms of the metal of the compound (C): ##STR00011##
11. The polycarbonate resin composition according to claim 10,
wherein a glass transition temperature of the polycarbonate resin
as measured by differential scanning calorimetric analysis is
single.
12. A method for producing a polycarbonate resin composition,
comprising: an addition step of adding at least one compound (C)
selected from the group consisting of compounds of Group I metals
of the long-form periodic table and compounds of Group II metals of
the long-form periodic table in an amount of 0.5 to 1.000 ppm by
weight in terms of the metal per 100 parts by weight of the total
amount of a polycarbonate resin (A) containing a constitutional
unit derived from a compound represented by the following formula
(1) and an aromatic polycarbonate resin (B), and a reaction step of
melt-reacting the polycarbonate resin (A) aromatic polycarbonate
resin (B) after the addition step: ##STR00012## wherein the melt
reaction is conducted under reduced pressure.
13. The method for producing a polycarbonate resin composition
according to claim 12, wherein the melt reaction in the reaction
step is carried out under the condition of a vacuum degree of 30
kPa or less.
14. The method for producing a polycarbonate resin composition
according to claim 12, wherein the compound (C) is at least one
member selected from the group consisting of an inorganic salt of a
carbonate, a carboxylate, a phenolate, a halogen compound and a
hydroxylated compound.
15. The method for producing a polycarbonate resin composition
according to claim 12, wherein the compound (C) is at least one
member selected from the group consisting of a sodium compound, a
potassium compound and a cesium compound.
16. The method for producing a polycarbonate resin composition
according to claim 12, wherein a crown ether compound (D) is
further added in the addition step and the amount added of the
crown ether compound (D) is from 0.1 to 10 times by mol relative to
the amount in terms of the metal of the compound (C).
17. The method for producing a polycarbonate resin composition
according to claim 12, wherein an acidic compound (E) is further
added in the addition step.
18. The method for producing a polycarbonate resin composition
according to claim 17, wherein an amount added of the acidic
compound (E) is from 0.1 to 5 times by mol relative to the amount
added of the metal in the compound (C).
Description
TECHNICAL FIELD
The present invention relates to a polycarbonate resin composition
having excellent transparency and possessing biogenic substance
content rate, heat resistance, wet heat resistance and impact
resistance in a balanced manner, a production method thereof, and a
molded body obtained by molding the resin composition.
BACKGROUND ART
Although a conventional aromatic polycarbonate resin containing a
structure originating in bisphenol A, etc. is produced by using a
raw material derived from petroleum resources, in recent years,
depletion of petroleum resources is concerned, and it is demanded
to provide a polycarbonate resin using a raw material obtained from
biomass resources such as plant. In addition, because of a concern
that global warming due to increase or accumulation of carbon
dioxide emissions may bring about climate change, etc., development
of a polycarbonate resin using a plant-derived monomer as a raw
material and being carbon neutral even when discarded after use is
demanded.
Under these circumstances, there has been proposed a method where
isosorbide (ISB) which is a dihydroxy compound obtained from
biomass resources is used as a monomer component and a
polycarbonate resin is obtained through transesterification with a
carbonic acid diester with distilling off a by-produced monohydroxy
compound under reduced pressure (see, for example, Patent Documents
1 to 7).
However, a dihydroxy compound such as ISB has low thermal
stability, in comparison with bisphenol compounds used for a
conventional aromatic polycarbonate resin, and there is a problem
that the resin is colored through thermal decomposition at the time
of polycondensation reaction, molding or processing, which are
performed at a high temperature. Furthermore, as for the copolymer
of ISB and a bisphenol compound described in Patent Documents 3 to
6, although a polymer having a high glass transition temperature is
obtained, on the other hand, the terminal of the polymer becomes a
bisphenol compound due to a difference between the reactivity of
ISB and the reactivity of a bisphenol compound and when a
polymerization temperature lower than the polymerization
temperature of an aromatic polycarbonate resin is selected in
consideration of color tone or thermal stability of ISB, a kind of
end capping occurs, as a result, the polymerization degree may not
sufficiently increase, resulting in a polymer having poor impact
resistance. This is conspicuous particularly when the
copolymerization amount of a bisphenol compound in the polymer is
20 mol % or more.
Furthermore, Patent Document 7 discloses a polycarbonate copolymer
containing a constitutional unit derived from ISB, a constitutional
unit derived from an aliphatic dihydroxy compound, and a
constitutional unit derived from an aromatic bisphenol compound.
However, this polycarbonate copolymer also contains a
constitutional unit derived from a bisphenol compound and although
the heat resistance, moldability and mechanical strength are
excellent, the degree of polymerization may not sufficiently
increase, resulting in a polymer having poor impact resistance. In
addition, the biogenic substance content rate is low, and this is
unfavorable in view of environment.
A polycarbonate resin composed of a dihydroxy compound such as
isosorbide (ISB) that is a dihydroxy compound obtained from biomass
resources, has a high glass transition temperature and excellent
heat resistance but is rigid and moreover, has drawbacks of high
melt viscosity at the time of melt polymerization and poor impact
resistance because polymer having a high molecular weight cannot be
obtained. In order to improve toughness, attempts are being made to
copolymerize an aliphatic dihydroxy compound or an aromatic
bisphenol compound.
Specifically, Patent Document 8 discloses a polycarbonate resin
composition containing a polycarbonate resin and an aromatic
polycarbonate resin, wherein the polycarbonate resin contains a
constitutional unit derived from ISB and a dihydroxy compound of an
aliphatic hydrocarbon and the content of a constitutional unit
derived from the dihydroxy compound of an aliphatic hydrocarbon is
45 mol % or more. Patent Document 9 discloses a polycarbonate resin
composition having excellent pencil hardness, which is obtained by
mixing an aromatic polycarbonate resin with a polycarbonate resin
containing a constitutional unit derived from ISB and a dihydroxy
compound of an aliphatic hydrocarbon.
BACKGROUND ART LITERATURE
Patent Document
Patent Document 1: WO 2004/111106
Patent Document 2: WO 2007/063823
Patent Document 3: WO 2005/066239
Patent Document 4: WO 2006/041190
Patent Document 5: JP-A-2009-062501
Patent Document 6: JP-A-2009-020963
Patent Document 7: JP-A-2011-127108
Patent Document 8: WO 2011/071162
Patent Document 9: WO 2012/111721
SUMMARY OF THE INVENTION
Problems that the Invention is to Solve
However, there is a problem that the copolymer of an aliphatic
dihydroxy compound has insufficient heat resistance, and the
copolymer of an aromatic bisphenol compound has high heat
resistance but is disadvantageous in that a polycarbonate resin
having a sufficient large molecular weight is not obtained due to a
problem of reactivity. Accordingly, although the resin composition
of Patent Document 8 containing an aromatic polycarbonate resin and
an ISB-copolymerized polycarbonate resin containing 45 mol % or
more of an aliphatic dihydroxy compound is excellent in the
transparency, hue, thermal stability, moldability and mechanical
strength, when, for example, a composition having a glass
transition temperature of 120.degree. C. or more is intended to
obtain so as to more increase the heat resistance, the content rate
of an aromatic polycarbonate resin in the polycarbonate resin
composition must be increased to 50% by weight or more. This means
a decrease in the biogenic substance content rate and is
unfavorable in view of environment. In the polycarbonate resin of
Patent Document 9 obtained by mixing an aromatic polycarbonate
resin with a polycarbonate resin containing a constitutional unit
derived from ISB and a dihydroxy compound of an aliphatic
hydrocarbon, the total light transmittance is substantially less
than 20%, giving rise to a problem that the transparency is
poor.
The present invention has been made in consideration of such a
background and intends to provide a polycarbonate resin composition
having excellent transparency and possessing high levels of
biogenic substance content rate, heat resistance, wet heat
resistance and impact resistance in a balanced manner, a production
method thereof, and a molded body of the polycarbonate resin
composition.
Means for Solving the Problems
As a result of many intensive studies to solve the problems above,
the present inventors have found that a polycarbonate resin
composition containing a specific polycarbonate resin (A) and an
aromatic polycarbonate resin (B) has excellent transparency and
possesses high levels of biogenic substance content rate, heat
resistance, wet heat resistance and impact resistance in a balanced
manner, and have arrived at the present invention. That is, the
gist of the present invention resides in the following [1] to [19].
[1] A polycarbonate resin composition comprising:
a polycarbonate resin (A) containing a constitutional unit derived
from a compound represented by the following formula (1),
an aromatic polycarbonate resin (B), and
at least one compound (C) selected from the group consisting of
compounds of Group I metals of the long-form periodic table and
compounds of Group II metals of the long-form periodic table,
wherein:
the content of the compound (C) per 100 parts by weight of the
total amount of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) is from 0.8 to 1,000 ppm by weight in terms
of the metal in the compound (C), and
the glass transition temperature as measured by differential
scanning calorimetric analysis is single:
##STR00002## [2] A polycarbonate resin composition comprising:
a polycarbonate resin (A) containing a constitutional unit derived
from a compound represented by the following formula (1),
an aromatic polycarbonate resin (B),
at least one compound (C) selected from the group consisting of
compounds of Group I metals of the long-form periodic table and
compounds of Group II metals of the long-form periodic table,
and
a crown ether compound (D),
wherein:
the content of the compound (C) per 100 parts by weight of the
total amount of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) is from 0.8 to 1,000 ppm by weight in terms
of the metal in the compound (C), and
the content of the crown ether compound (D) is from 0.1 to 10 times
by mol relative to the amount in terms of the metal of the compound
(C):
##STR00003## [3] The polycarbonate resin composition according to
the above [2], wherein the glass transition temperature as measured
by differential scanning calorimetric analysis is single. [4] The
polycarbonate resin composition according to any one of the above
[1] to [3], wherein the total light transmittance of a molded body
having a thickness of 2 mm obtained by molding the polycarbonate
resin composition is 80% or more. [5] The polycarbonate resin
composition according to any one of the above [1] to [4], wherein
the composition contains a Group I metal of the long-form periodic
table and a Group II metal of the long-form period table. [6] The
polycarbonate resin composition according to any one of the above
[1] to [5], wherein the composition contains, as the compound (C),
at least a compound of a Group I metal of the long-form periodic
table and the content of the compound of a Group I metal of the
long-form period table per 100 parts by weight of the total amount
of the polycarbonate resin (A) and the aromatic polycarbonate resin
(B) is from 0.8 to 1,000 ppm by weight in terms of the metal. [7]
The polycarbonate resin composition according to any one of the
above [1] to [6], wherein the compound (C) is at least one member
selected from the group consisting of an inorganic salt (including
a carbonate), a carboxylate, a phenolate, a halogen compound and a
hydroxylated compound. [8] The polycarbonate resin composition
according to any one of the above [1] to [7], wherein the compound
(C) is at least one member selected from the group consisting of a
sodium compound, a potassium compound and a cesium compound. [9]
The polycarbonate resin composition according to any one of the
above [1] to [8], further comprising an acidic compound (E). [10]
The polycarbonate resin composition according to the above [9],
wherein the content of the acidic compound (E) is from 0.1 to 5
times by mol relative to the content of the metal in the compound
(C). [11] A molding body comprising the polycarbonate resin
composition according to any one of the above [1] to [10]. [12] A
method for producing a polycarbonate resin composition,
comprising:
an addition step of adding at least one compound (C) selected from
the group consisting of compounds of Group I metals of the
long-form periodic table and compounds of Group II metals of the
long-form periodic table in an amount of 0.5 to 1,000 ppm by weight
in terms of the metal per 100 parts by weight of the total amount
of a polycarbonate resin (A) containing a constitutional unit
derived from a compound represented by the following formula (1)
and an aromatic polycarbonate resin (B), and
a reaction step of melt-reacting the polycarbonate resin (A) with
the aromatic polycarbonate resin (B) after the addition step:
##STR00004## [13] the Method for Producing a Polycarbonate Resin
Composition According to the Above [12], wherein the melt reaction
in the reaction step is performed under reduced pressure. [14] The
method for producing a polycarbonate resin composition according to
the above [12] or [13], wherein the melt reaction in the reaction
step is carried out under the condition of a vacuum degree of 30
kPa or less. [15] The method for producing a polycarbonate resin
composition according to any one of the above [12] to [14], wherein
the compound (C) is at least one member selected from the group
consisting of an inorganic salt (including a carbonate), a
carboxylate, a phenolate, a halogen compound and a hydroxylated
compound. [16] The method for producing a polycarbonate resin
composition according to any one of the above [12] to [15], wherein
the compound (C) is at least one member selected from the group
consisting of a sodium compound, a potassium compound and a cesium
compound. [17] The method for producing a polycarbonate resin
composition according to any one of the above [12] to [16], wherein
a crown ether compound (D) is further added in the addition step
and the amount added of the crown ether compound (D) is from 0.1 to
10 times by mol relative to the amount in terms of the metal of the
compound (C). [18] The method for producing a polycarbonate resin
composition according to any one of the above [12] to [17], wherein
an acidic compound (E) is further added in the addition step. [19]
The method for producing a polycarbonate resin composition
according to the above [18], wherein the amount added of the acidic
compound (E) is from 0.1 to 5 times by mol relative to the amount
added of the metal in the compound (C).
Effect of the Invention
The polycarbonate resin composition and its molded body of the
present invention have excellent transparency and possess high
levels of biogenic substance content rate, heat resistance, wet
heat resistance and impact resistance in a balanced manner. The
polycarbonate resin composition of the present invention is
obtained by performing an addition step and a reaction step as
described above.
MODE FOR CARRYING OUT THE INVENTION
Although the mode for carrying out the present invention is
described in detail below, the following descriptions of
constituent elements are an example (representative example) of the
embodiment of the present invention and as long as its gist is
observed, the present invention is not limited to the contents
below.
[Polycarbonate Resin (A)]
The polycarbonate resin (A) contains a constitutional unit derived
from a dihydroxy compound represented by the following formula (1)
(this unit is appropriately referred to as "constitutional unit
(a)"). The polycarbonate resin (A) may be a homopolycarbonate resin
of the constitutional unit (a) or may be a polycarbonate resin
obtained by copolymerizing a constitutional unit other than the
constitutional unit (a). In view of higher impact resistance, a
copolymerized polycarbonate resin is preferred.
##STR00005##
The dihydroxy compound represented by formula (1) includes
isosorbide (ISB), isomannide, and isoidetto, which are in a
stereoisomeric relationship. One of these may be used alone, or two
or more thereof may be used in combination.
Among the dihydroxy compounds represented by formula (1),
isosorbide (ISB) obtained by dehydration condensation of sorbitol
produced from various starches existing abundantly as plant-derived
resources and being easily available is most preferred in terms of
availability, ease of production, weather resistance, optical
properties, moldability, heat resistance and carbon neutrality.
The dihydroxy compound represented by formula (1) tends to be
gradually oxidized by oxygen. Accordingly, during storage or in
handling at the time of production, it is preferable to allow no
mingling of water for preventing decomposition due to oxygen or to
use a deoxidizer or create a nitrogen atmosphere.
The polycarbonate resin (A) is preferably a copolymerized
polycarbonate resin containing a constitutional unit (a) derived
from a dihydroxy compound represented by formula (1) and a
constitutional unit derived from one or more dihydroxy compounds
selected from the group consisting of a dihydroxy compound of an
aliphatic hydrocarbon, a dihydroxy compound of an alicyclic
hydrocarbon, and an ether-containing dihydroxy compound (this
constitutional unit is appropriately referred to as "constitutional
unit (b)"). These dihydroxy compounds have a flexible molecular
structure and therefore, when such a dihydroxy compound is used as
a raw material, the toughness of the obtained polycarbonate resin
(A) can be enhanced. Among these dihydroxy compounds, a dihydroxy
compound of a aliphatic hydrocarbon and a dihydroxy compound of an
alicyclic hydrocarbon, each having a large effect of enhancing the
toughness, are preferably used, and use of a dihydroxy compound of
an alicyclic hydrocarbon is most preferred. Specific examples of
the dihydroxy compound of an aliphatic hydrocarbon, the dihydroxy
compound of an alicyclic hydrocarbon, and the ether-containing
dihydroxy compound are as follows.
As the dihydroxy compound of an aliphatic hydrocarbon, for example,
the following dihydroxy compounds can be employed: a linear
aliphatic dihydroxy compound such as ethylene glycol,
1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol,
1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and
1,12-dodecanediol; and an aliphatic dihydroxy compound having a
branched chain, such as 1,3-butanediol, 1,2-butanediol, neopentyl
glycol and hexylene glycol.
As the dihydroxy compound of an alicyclic hydrocarbon, for example,
the following dihydroxy compounds can be employed: a dihydroxy
compound that is a primary alcohol of an alicyclic hydrocarbon, as
exemplified by, e.g., a dihydroxy compound derived from a terpene
compound, such as 1,2-cyclohexane dimethanol, 1,3-cyclohexane
dimethanol, 1,4-cyclohexane dimethanol, tricyclodecane dimethanol,
pentacyclopentadecane dimethanol, 2,6-decalin dimethanol,
1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbomane
dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol
and limonene; and a dihydroxy compound that is a secondary or
tertiary alcohol of an alicyclic hydrocarbon, as exemplified by,
e.g., 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol,
hydrogenated bisphenol A, and
2,2,4,4-tetramethyl-1,3-cyclobutanediol.
The ether-containing dihydroxy compounds includes oxyalkylene
glycols and a dihydroxy compound containing an acetal ring.
As the oxyalkylene glycols, for example, diethylene glycol,
triethylene glycol, tetraethylene glycol, polyethylene glycol, and
polypropylene glycol may be employed.
As the dihydroxy compound containing an acetal ring, for example, a
spiroglycol represented by the following structural formula (2),
and a dioxane glycol represented by the following structural
formula (3) may be employed.
##STR00006##
In the polycarbonate resin (A), the content ratio of the
constitutional unit (a) relative to 100 mol % of constitutional
units derived from all dihydroxy compounds is not particularly
limited but is preferably more than 40 mol %, more preferably more
than 50 mol %, still more preferably from 55 to 95 mol %, yet still
more preferably from 60 to 90 mol %, and most preferably from 65 to
85 mol %. In such a case, the biogenic substance content rate can
be more increased, and the heat resistance can be more enhanced.
The content ratio of the constitutional unit (a) in the
polycarbonate resin (A) may be 100 mol %, but from the viewpoint of
more increasing the molecular weight and from the viewpoint of more
enhancing the impact resistance, a constitutional unit other than
the constitutional unit (a) is preferably copolymerized in the
polycarbonate resin (A).
The polycarbonate resin (A) may further contain a constitutional
unit other than the constitutional unit (a) and the constitutional
unit (b). As such a constitutional unit (other dihydroxy
compounds), for example, a dihydroxy compound containing an
aromatic group may be employed. However, if a large amount of a
constitutional unit derived from a dihydroxy compound containing an
aromatic group is contained in the polycarbonate resin (A), for the
reason above, a polycarbonate resin (A) having a high molecular
weight is not obtained, and the effect of enhancing the impact
resistance may decrease. Accordingly, from the viewpoint of more
enhancing the impact resistance, the content ratio of the
constitutional unit derived from a dihydroxy compound containing an
aromatic group is preferably 10 mol % or less, more preferably 5
mol % or less, relative to 100 mol % of constitutional units
derived from all dihydroxy compounds.
As the dihydroxy compound containing an aromatic group, for
example, the following dihydroxy compounds can be employed, but a
dihydroxy compound other than these may also be employed: an
aromatic bisphenol compound such as
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
2,2-bis(4-hydroxy-3,5-diethylphenyl)propane,
2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane,
2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
bis(4-hydroxyphenyl)diphenylmethane,
1,1-bis(4-hydroxyphenyl)-2-ethylhexane,
1,1-bis(4-hydroxyphenyl)decane,
bis(4-hydroxy-3-nitrophenyl)methane,
3,3-bis(4-hydroxyphenyl)pentane,
1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene,
1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone,
2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxy-3-methylphenyl)sulfide,
bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether and
4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; a dihydroxy compound
having an ether group bonded to an aromatic group, such as
2,2-bis(4-(2-hydroxyethoxy)phenyl)propane,
2,2-bis(4-(2-hydroxypropoxy)phenyl)propane,
1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl,
bis(4-(2-hydroxyethoxy)phenyl)sulfone; and a dihydroxy compound
having a fluorene ring, such as
9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene,
9,9-bis(4-hydroxyphenyl)fluorene,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene,
9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene
and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene.
The other dihydroxy compound may be appropriately selected
according to the properties required of the polycarbonate resin
(A). Only one of other dihydroxy compounds recited above may be
used, or a plurality of kinds thereof may be used in combination.
When the other dihydroxy compound is used in combination with the
dihydroxy compound represented by formula (1), an effect of, for
example, improving the flexibility or mechanical properties of the
polycarbonate resin (A) or improving the moldability can be
obtained.
The dihydroxy compound used as a raw material of the polycarbonate
resin (A) may contain a stabilizer such as reducing agent,
antioxidant, deoxidizer, light stabilizer, antacid, pH stabilizer
and heat stabilizer. In particular, the dihydroxy compound
represented by formula (1) is susceptible to a change in quality
under acidic conditions. Accordingly, the change in quality of the
dihydroxy compound represented by formula (1) can be suppressed by
using a basic stabilizer in the process of synthesizing the
polycarbonate resin (A) and in turn, the quality of the obtained
polycarbonate resin composition can be more enhanced.
As the basic stabilizer, for example, the following compounds can
be employed: hydroxides, carbonates, phosphates, phosphites,
hypophosphites, borates and fatty acid salts of Group I or Group II
metals in the long-form periodic table (Nomenclature of Inorganic
Chemistry IUPAC Recommendations 2005); a basic ammonium compound
such as tetramethylammonium hydroxide, tetraethylammonium
hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium
hydroxide, trimethylethylammonium hydroxide,
trimethylbenzylammonium hydroxide, trimethylphenyl ammonium
hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium
hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium
hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium
hydroxide, benzyltriphenylammonium hydroxide, methyltriphenyl
ammonium hydroxide and butyltriphenylammonium hydroxide; an
amine-based compound such as diethylamine, dibutylamine,
triethylamine, morpholine, N-methylmorpholine, pyrrolidine,
piperidine, 3-amino-1-propanol, ethylenediamine,
N-methyldiethanolamine, diethyl ethanolamine, diethanolamine,
triethanolamine, 4-aminopyridine, 2-aminopyridine,
N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine,
2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine,
2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole,
2-mercaptoimidazole, 2-methylimidazole and aminoquinoline; and a
hindered amine-based compound such as di-(tert-butyl)amine and
2,2,6,6-tetramethylpiperidine.
Although the content of the basic stabilizer in the dihydroxy
compound is not particularly limited, since the dihydroxy compound
represented by formula (1) is unstable in the acidic state, the
content of the basic stabilizer is preferably set such that the pH
of an aqueous solution of the dihydroxy compound containing the
basic stabilizer becomes around 7.
The content of the basic stabilizer relative to the dihydroxy
compound represented by formula (1) is preferably from 0.0001 to 1%
by weight. In this case, the effect of preventing a change in
quality of the dihydroxy compound represented by formula (1) is
sufficiently obtained. From the viewpoint of more increasing this
effect, the content of the basic stabilizer is more preferably from
0.001 to 0.1% by weight.
As the carbonic acid diester used as a raw material of the
polycarbonate resin (A), usually, a compound represented by the
following formula (4) may be employed. One of these carbonic acid
diesters may be used alone, or two or more thereof may be used in
combination.
##STR00007##
In formula (4), each of A.sup.1 and A.sup.2 is a substituted or
unsubstituted aliphatic hydrocarbon group having a carbon number of
1 to 18 or a substituted or unsubstituted aromatic hydrocarbon
group, and A.sup.1 and A.sup.2 may be the same or different. As
A.sup.1 and A.sup.2, a substituted or unsubstituted aromatic
hydrocarbon group is preferably employed, and it is more preferable
to employ an unsubstituted aromatic hydrocarbon group.
As the carbonic acid diester represented by formula (4), for
example, a substituted diphenyl carbonate such as diphenyl
carbonate (DPC) and ditolyl carbonate, a dimethyl carbonate, a
diethyl carbonate, and a di-tert-butyl carbonate may be employed.
Among these carbonic acid diesters, a diphenyl carbonate and a
substituted diphenyl carbonate are preferably used, and it is more
preferable to use a diphenyl carbonate. Incidentally, the carbonic
acid diester sometimes contains impurities such as chloride ion,
and since the impurities may inhibit the polycondensation reaction
or cause deterioration of the color tone of the obtained
polycarbonate resin (A), it is preferable to use a carbonic acid
diester purified as needed by distillation, etc.
The polycarbonate resin (A) can be synthesized by polycondensation
through a transesterification reaction of the above-described
dihydroxy compound and carbonic acid diester. More specifically,
the polycarbonate resin can be obtained by allowing, in the course
of polycondensation, a monohydroxy compound, etc. by-produced
during the transesterification reaction to be removed out of the
system.
The transesterification reaction proceeds in the presence of a
transesterification reaction catalyst (hereinafter, the
transesterification catalyst is referred to as "polymerization
catalyst"). The kind of the polymerization catalyst may very
greatly affect the reaction rate of the transesterification
reaction and the quality of the obtained polycarbonate resin
(A).
The polymerization catalyst is not limited as long as the
transparency, color tone, heat resistance, weather resistance and
mechanical strength of the obtained polycarbonate resin (A) can be
satisfied. As the polymerization catalyst, for example, a compound
of a metal of Group I or Group II (in general, sometimes denoted as
Group 1 or Group 2 in the long-form periodic table but hereinafter,
is denoted simply as "Group 1" or "Group 2"), and a basic compound
such as basic boron compound, basic phosphorus compound, basic
ammonium compound and amine-based compound, may be used, and among
these, a Group 1 metal compound and/or a Group 2 metal compound are
preferred.
As the Group 1 metal compound, for example, the following compounds
can be employed: sodium hydroxide, potassium hydroxide, lithium
hydroxide, cesium hydroxide, sodium hydrogencarbonate, potassium
hydrogencarbonate, lithium hydrogencarbonate, cesium
hydrogencarbonate, sodium carbonate, potassium carbonate, lithium
carbonate, cesium carbonate, sodium acetate, potassium acetate,
lithium acetate, cesium acetate, sodium stearate, potassium
stearate, lithium stearate, cesium stearate, sodium borohydride,
potassium borohydride, lithium borohydride, cesium borohydride,
sodium borophenylate, potassium borophenylate, lithium
borophenylate, cesium borophenylate, sodium benzoate, potassium
benzoate, lithium benzoate, cesium benzoate, disodium
hydrogenphosphate, dipotassium hydrogenphosphate, dilithium
hydrogenphosphate, dicesium hydrogenphosphate, disodium
phenylphosphate, dipotassium phenylphosphate, dilithium
phenylphosphate, dicesium phenylphosphate, an alcoholate or
phenolate of sodium, potassium, lithium and cesium, disodium,
dipotassium, dilithium and dicesium salts of bisphenol A, etc.
As the Group 1 metal compound, in view of polymerization activity
and color tone of the obtained polycarbonate resin (A), a lithium
compound is preferred.
As the Group 2 metal compound, for example, the following compounds
can be employed: calcium hydroxide, barium hydroxide, magnesium
hydroxide, strontium hydroxide, calcium hydrogencarbonate, barium
hydrogencarbonate, magnesium hydrogencarbonate, strontium
hydrogencarbonate, calcium carbonate, barium carbonate, magnesium
carbonate, strontium carbonate, calcium acetate, barium acetate,
magnesium acetate, strontium acetate, calcium stearate, barium
stearate, magnesium stearate, strontium stearate, etc.
From the viewpoint that the transparency, initial Haze (haze) and
impact resistance of a molded body obtained by molding the
polycarbonate resin composition can be more enhanced, the
polymerization catalyst is more preferably a Group 2 metal
compound. From the viewpoint that the transparency, initial Haze
(haze) and impact resistance of a molded body obtained by molding
the polycarbonate resin composition can be further more enhanced,
the Group 2 metal compound is preferably a magnesium compound, a
calcium compound, or a barium compound. In view of the
polymerization activity and color tone of the obtained
polycarbonate resin (A), a magnesium compound and/or a calcium
compound are more preferred, and a calcium compound is most
preferred.
Incidentally, together with the Group 1 metal compound and/or the
Group 2 metal compound, a basic compound such as basic boron
compound, basic phosphorus compound, basic ammonium compound and
amine-based compound may be secondarily used in combination, and it
is particularly preferable to use only a Group 1 metal compound
and/or a Group 2 metal compound.
As the basic phosphorus compound, for example, the following
compounds can be employed: triethylphosphine,
tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,
triphenylphosphine, tributylphosphine, a quaternary phosphonium
salt, etc.
As the basic ammonium compound, for example, the following
compounds can be employed: tetramethylammonium hydroxide,
tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
tetrabutylammonium hydroxide, trimethyl ethylammonium hydroxide,
trimethylbenzylammonium hydroxide, trimethylphenylammonium
hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium
hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium
hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium
hydroxide, benzyltriphenylammonium hydroxide,
methyltriphenylammonium hydroxide, butyltriphenylammonium
hydroxide, etc.
As the amine-based compound, for example, the following compounds
can be employed: 4-aminopyridine, 2-aminopyridine,
N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine,
2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine,
2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole,
2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, guanidine,
etc.
The amount of the polymerization catalyst used is preferably from
0.1 to 300 .mu.mol, more preferably from 0.5 to 100 .mu.m, still
more preferably from 1 to 50 .mu.mol, per mol of all dihydroxy
compounds used for the reaction.
In the case of using, as the polymerization catalyst, a compound
containing a Group 2 metal in the long-form periodic table,
particularly in the case of using a magnesium compound and/or a
calcium compound, the amount of the polymerization catalyst used is
preferably 0.1 .mu.mol or more, more preferably 0.3 .mu.mol or
more, still more preferably 0.5 .mu.mol or more, per mol of all
dihydroxy compounds used for the reaction. The upper limit is
preferably 10 .mu.mol or less, more preferably 5 .mu.mol or less,
still more preferably 3 .mu.m or less.
Incidentally, unless a special purification operation is performed,
the compound used as a catalyst at the time of polymerization
remains also in the polycarbonate resin itself, and the amount
thereof is the same as the amount used at the time of
production.
When the amount of the polymerization catalyst used is adjusted to
the range above, the polymerization rate can be increased, so that
a polycarbonate resin (A) having a desired molecular weight can be
obtained by not necessarily raising the polymerization temperature,
as a result, deterioration of the color tone of the polycarbonate
resin (A) can be suppressed. In addition, the molar ratio between
the dihydroxy compound and the carbonic acid diester can be
prevented from being disrupted due to volatilization of an
unreacted raw material in the middle of polymerization and
therefore, a resin having a desired molecular weight can be more
reliably obtained. Furthermore, occurrence of a parallel side
reaction can be suppressed, so that deterioration of the color tone
of the polycarbonate resin (A) or coloring at the time of molding
and processing can be more successfully prevented.
Among the Group 1 metals, considering an adverse effect of sodium,
potassium or cesium on the color tone of the polycarbonate resin
(A) or an adverse effect of iron on the color tone of the
polycarbonate resin (A), the total content of sodium, potassium,
cesium and iron in the polycarbonate resin (A) is preferably 1 ppm
by weight or less. In this case, deterioration of the color tone of
the polycarbonate resin (A) can be more successfully prevented, and
the color tone of the polycarbonate resin (A) can be more improved.
From the same viewpoint, the total content of sodium, potassium
cesium and iron in the polycarbonate resin (A) is more preferably
0.5 ppm by weight or less. Incidentally, such a metal may get mixed
in not only from the catalyst used but also from a raw material or
a reaction apparatus. Irrespective of the source, the total amount
of compounds of these metals in the polycarbonate resin (A) is
preferably adjusted to fall in the above-described range in terms
of the total content of sodium potassium, cesium and iron.
(Synthesis of Polycarbonate Resin (A))
The polycarbonate resin (A) is obtained by polycondensation through
a transesterification reaction of a dihydroxy compound used as a
raw material, like e.g. a dihydroxy compound represented by formula
(1), with a carbonic acid diester in the presence of a
polymerization catalyst.
The dihydroxy compound as a raw material and the carbonic acid
diester are preferably mixed uniformly before the
transesterification reaction. The mixing temperature is usually
80.degree. C. or more, preferably 90.degree. C. or more, and is
usually 250.degree. C. or less, preferably 200.degree. C. or less,
more preferably 150.degree. C. or less, and above all, a mixing
temperature of 100 to 120.degree. C. is suitable. In this case, the
dissolution rate may be increased or the solubility may be
sufficiently enhanced, and a trouble such as solidification can be
fully avoided. Furthermore, in this case, thermal deterioration of
the dihydroxy compound may be fully avoided, as a result, the color
tone of the obtained polycarbonate resin (A) can be more improved
and at the same time, the weather resistance can also be
enhanced.
The operation of mixing the dihydroxy compound as a raw material
and the carbonic acid diester is preferably performed in an
atmosphere having an oxygen concentration of 10 vol % or less,
particularly from 0.0001 to 10 vol %, more particularly from 0.0001
to 5 vol %, still more particularly from 0.0001 to 1 vol %. In this
case, the color tone can be more improved and at the same time, the
reactivity can be increased.
For obtaining the polycarbonate resin (A), the carbonic acid
diester is preferably used in a molar ratio of 0.90 to 1.20
relative to all dihydroxy compounds used for the reaction. In this
case, an increase in the amount of the terminal hydroxyl group of
the polycarbonate resin (A) can be suppressed, so that the thermal
stability of the polymer can be improved. Accordingly, coloring at
the time of molding can be more successfully prevented or the rate
of the transesterification reaction can be enhanced. In addition, a
desired high-molecular-weight form can be more reliably obtained.
Furthermore, when the amount of the carbonic acid diester used is
adjusted to fall in the range above, a decrease in the
transesterification reaction rate can be suppressed, and a
polycarbonate resin (A) having a desired molecular weight can be
more reliably produced. In this case, the thermal history at the
time of reaction can also be prevented from increasing, and the
color tone or weather resistance of the polycarbonate resin (A) can
therefore be more improved. Also, in this case, the amount of the
carbonic acid diester remaining in the polycarbonate resin (A) can
be decreased, and staining or odor generation during molding can be
avoided or reduced. From the same viewpoint as above, the amount of
the carbonic acid diester used is more preferably, in terms of the
molar ratio, from 0.95 to 1.10 relative to all dihydroxy
compounds.
As the method for polycondensation of the dihydroxy compound and
the carbonic acid diester, the reaction is conducted in multiple
stages by using a plurality of reactors in the presence of the
above-described catalyst. The reaction mode includes a batch mode,
a continuous mode, and a method combining a batch mode and a
continuous mode, and it is preferable to employ a continuous mode
where the polycarbonate resin (A) is obtained with less thermal
history and the productivity is excellent.
In view of the control of the polymerization rate or the quality of
the obtained polycarbonate resin (A), it is important to
appropriately select the jacket temperature, the internal
temperature and the pressure in the reaction system according to
the reaction stage. Specifically, the polycondensation reaction is
preferably performed at relatively low temperature and low vacuum
in the initial stage of the reaction to obtain a prepolymer and
performed at relatively high temperature and high vacuum in the
later stage of the reaction to increase the molecular weight to a
predetermined value. In this case, the molar ratio between the
dihydroxy compound and the carbonic acid diester is easily adjusted
to a desired ratio by suppressing distillation of an unreacted
monomer. As a result, the polymerization rate can be prevented from
decreasing. In addition, a polymer having desired molecular weight
or terminal group can be more reliably obtained.
The polymerization rate in the polycondensation reaction is
controlled by the balance between the terminal hydroxy group and
the terminal carbonate group. Accordingly, when the balance of the
terminal groups fluctuates due to distillation of an unreacted
monomer, the polymerization rate can be hardly controlled to be
constant, and the molecular weight of the obtained resin may
largely fluctuate. Since the molecular weight of the resin
correlates with the melt viscosity, the melt viscosity may
fluctuate at the time of melt-processing the obtained resin, making
it difficult to keep the quality of the molded article constant.
Such a problem is likely to occur particularly when the
polycondensation reaction is performed in a continuous mode.
Use of a reflux condenser in a polymerization reactor is effective
for reducing the amount of an unreacted monomer distilled, and the
effect thereof is high particularly in the initial stage of the
reaction where the amount of an unreacted monomer is large. The
temperature of a refrigerant introduced into the reflux condenser
may be appropriately selected according to the monomer used, and
the temperature of the refrigerant introduced into the reflux
condenser is, at the inlet of the reflux condenser, usually from 45
to 180.degree. C., preferably from 80 to 150.degree. C., more
preferably from 100 to 130.degree. C. When the temperature of the
refrigerant is adjusted to fall in the range above, the effect
thereof is fully obtained by sufficiently increasing the reflux
volume and at the same time, distillation efficiency for the
monohydroxy compound that should be removed by distillation can be
sufficiently enhanced. As a result, reduction in the reaction rate
can be prevented, and coloring of the obtained resin can be more
successfully prevented. As the refrigerant, warm water, steam,
heating medium oil, etc. are used, and steam or heating medium oil
is preferred.
In order to more improve the color tone of the obtained
polycarbonate resin (A) with appropriately maintaining the
polymerization rate and suppressing distillation of a monomer,
selection of the kind and amount of the above-described
polymerization catalyst is important.
The polycarbonate resin (A) is produced using a polymerization
catalyst through a step usually having two or more stages. The
polycondensation reaction may be performed using one
polycondensation reactor through a step having two or more stages
by sequentially changing the conditions, and in view of production
efficiency, the reaction is preferably performed in multiple stages
by using a plurality of reactors and changing the conditions in
respective reactors.
From the viewpoint of efficiently performing the polycondensation
reaction, in the initial stage where the content of a monomer in
the reaction solution is large, it is important to suppress
volatilization of the monomer with maintaining a necessary
polymerization rate. In the later stage of the reaction, the matter
of importance is to sufficiently distill off a monohydroxy compound
being generated as a byproduct and thereby shift the equilibrium to
the polycondensation reaction side. Accordingly, reaction
conditions suitable for the initial stage of the reaction are
usually different from the reaction conditions suitable for the
later stage of the reaction. For this reason, a plurality of
reactors arranged in series are used, whereby the conditions in
respective reactors can be easily changed and the production
efficiency can be enhanced.
The number of polymerization reactors used in the production of the
polycarbonate resin (A) may be at least 2 as described above, and
in view of production efficiency, etc., the number of reactors is
preferably 3 or more, more preferably from 3 to 5, still more
preferably 4. When two or more polymerization reactors are used, a
plurality of reaction stages differing in the conditions may be
further performed in each polymerization reactor, or the
temperature and pressure may be continuously changed.
The polymerization catalyst may be added to a raw material
preparation tank or a raw material storage tank or may be added
directly to a polymerization tank. From the viewpoint of the
feeding stability and controlling the polycondensation reaction,
the polymerization catalyst is preferably fed in the form of an
aqueous solution by disposing a catalyst feed line in the middle of
a raw material line before it is fed to a polymerization
reactor.
When the temperature of the polycondensation reaction is adjusted,
this makes it possible to enhance the productivity or avoid an
increase in the thermal history of the product. Furthermore,
volatilization of a monomer or decomposition or coloring of the
polycarbonate resin (A) can be more successfully prevented.
Specifically, as the reaction conditions in the first stage
reaction, the following conditions can be employed. That is, the
internal temperature of the polymerization reactor is set to a
range of usually from 150 to 250.degree. C., preferably from 160 to
240.degree. C., and more preferably from 170 to 230.degree. C. The
pressure (hereinafter, the pressure indicates an absolute pressure)
of the polymerization reactor is set to a range of usually from 1
to 110 kPa, preferably from 5 to 70 kPa, and more preferably from 7
to 30 kPa. The reaction time is set to a range of usually from 0.1
to 10 hours, preferably from 0.5 to 3 hours. The first stage
reaction is preferably conducted with removing the generated
monohydroxy compound by distillation from the reaction system.
The reaction in the second and subsequent stages is preferably
performed by gradually lowering the pressure of the reaction system
from the pressure in the first stage and with continuously removing
the generated monohydroxy compound out of the reaction system,
finally setting the pressure (absolute pressure) of the reaction
system to 1 kPa or less. The maximum internal temperature of the
polymerization reactor is set to the range of usually from 200 to
260.degree. C., and preferably from 210 to 250.degree. C. The
reaction time is set to the range of usually from 0.1 to 10 hours,
preferably from 0.3 to 6 hours, and more preferably from 0.5 to 3
hours.
From the viewpoint of more suppressing coloring or thermal
degradation of the polycarbonate resin (A) and obtaining a
polycarbonate resin (A) having a better color tone, the maximum
internal temperature of the polymerization reactor in all reaction
stages is preferably set to the range of 210 to 240.degree. C. In
order to prevent a drop of the polymerization rate in the latter
half of the reaction and minimize the degradation due to thermal
history, a horizontal reactor excellent in the plug-flow properties
and interface renewal properties is preferably used in the final
stage of the polycondensation reaction.
In the continuous polymerization, for controlling the molecular
weight of the finally obtained polycarbonate resin (A) at a certain
level, the polymerization rate is preferably adjusted as needed. In
this case, the method having good operability is to adjust the
pressure of the polymerization reactor in the final stage.
In addition, since the polymerization rate changes according to the
ratio between the terminal hydroxy group and the terminal carbonate
group as described above, the polymerization rate is daringly
suppressed by decreasing the proportion of one terminal group, and
the pressure of the polymerization reactor in the final stage is
maintained at a high vacuum to that extent, whereby the content of
low molecular components remaining in the resin, including a
monohydroxy compound, can be decreased. However, in this case, if
the proportion of one terminal is too small, only with slight
fluctuation of the terminal group balance, the reactivity extremely
lowers, and the molecular weight of the obtained polycarbonate
resin (A) may not reach the desired molecular weight. In order to
avoid such a problem, the polycarbonate resin (A) obtained in the
polymerization reactor of the final stage preferably contains a
terminal hydroxy group and a terminal carbonate group both in an
amount of 10 mol/ton or more. On the other hand, if the contents of
both terminal groups are too large, the polymerization rate
increases, and the molecular weight becomes too high. For this
reason, the content of one terminal group is preferably 60 mol/ton
or less.
The amount of the terminal group and the pressure of the
polymerization reactor in the final stage are thus adjusted to
preferable ranges, and the residual amount of a monohydroxy
compound in the resin can thereby be decreased at the outlet of the
polymerization reactor. The residual amount of a monohydroxy group
in the resin at the outlet of the polymerization reactor is
preferably 2,000 ppm by weight or less, more preferably 1,500 ppm
by weight or less, still more preferably 1,000 ppm by weight or
less. By decreasing the content of a monohydroxy compound at the
outlet of the polymerization reactor in this way, devolatilization
of a monohydroxy compound, etc. can be easily performed in the
later step.
Although the residual amount of a monohydroxy compound is
preferably smaller, when it is intended to decrease the residual
amount to less than 100 ppm by weight, this requires to employ
operating conditions such that the amount of one terminal group is
extremely reduced and the pressure of a polymerization reactor is
thereby maintained at a high vacuum. In this case, as described
above, the molecular weight of the finally obtained polycarbonate
resin (A) can be hardly kept at a certain level, and for this
reason, the residual amount of a monohydroxy compound is usually
100 ppm by weight or more, preferably 150 ppm by weight or
more.
From the viewpoint of effectively utilizing resources, the
byproduct monohydroxy compound is preferably purified, if desired,
and then reused as a raw material of other compounds. For example,
in the case where the monohydroxy compound is phenol, the phenol
can be used as a raw material of diphenyl carbonate, bisphenol A,
etc.
The glass transition temperature of the polycarbonate resin (A) is
preferably 90.degree. C. or more. In this case, the heat resistance
and the biogenic substance content rate of the polycarbonate resin
composition can be enhanced in a balanced manner. From the same
viewpoint, the glass transition temperature of the polycarbonate
resin (A) is more preferably 100.degree. C. or more, still more
preferably 110.degree. C. or more, yet still more preferably
120.degree. C. or more. On the other hand, the glass transition
temperature of the polycarbonate resin (A) is preferably
170.degree. C. or less. In this case, the melt viscosity can be
reduced by the above-described melt polymerization, and a polymer
having an adequate molecular weight can be obtained. In addition,
if it is intended to increase the molecular weight by raising the
polymerization temperature and in turn, lowering the melt
viscosity, since the heat resistance of the constitutional
component (a) is not sufficient, the resin may be readily colored.
From the viewpoint that the growth of molecular weight and the
prevention of coloring can be more enhanced in a balanced manner,
the glass transition temperature of the polycarbonate resin (A) is
more preferably 165.degree. C. or less, still more preferably
160.degree. C. or less, and yet still more preferably 150.degree.
C. or less.
The molecular weight of the polycarbonate resin (A) can be
expressed by the reduced viscosity, and a higher reduced viscosity
indicates a larger molecular weight. The reduced viscosity is
usually 0.30 dL/g or more, and preferably 0.33 dL/g or more. In
this case, the mechanical strength of a molded article can be more
enhanced. On the other hand, the reduced viscosity is usually 1.20
dL/g or less, preferably 1.00 dL/g or less, and more preferably
0.80 dL/g or less. In this case, the flowability during molding can
be enhanced, and the productivity or moldability can be more
improved. The reduced viscosity of the polycarbonate resin (A) as
used herein is a value when a solution prepared by using methylene
chloride as a solvent and precisely adjusting the concentration of
the resin composition to 0.6 g/dL is measured by an Ubbelohde
viscometer under the condition of a temperature of 20.0.degree.
C..+-.0.1.degree. C. Details of the method for measuring the
reduced viscosity and described in Examples.
The melt viscosity of the polycarbonate resin (A) is preferably
from 400 to 3,000 Pas. In this case, a molded article of the resin
composition can be prevented from becoming brittle, and the
mechanical properties can be more enhanced. Furthermore, in this
case, the flowability at the time of molding and processing can be
enhanced, making it possible to prevent degradation of the
appearance of a molded article or deterioration of the dimensional
accuracy. Moreover, in this case, coloring or bubbling resulting
from a rise of the resin temperature due to shear heating can be
more successfully prevented. From the same viewpoint, the melt
viscosity of the polycarbonate resin (A) is more preferably from
600 to 2,500 Pas, and still more preferably from 800 to 2,000 Pas.
The melt viscosity as used in the present description indicates a
melt viscosity at a temperature of 240.degree. C. and a shear rate
of 91.2 sec.sup.-1 as measured by using a capillary rheometer
[manufactured by Toyo Seiki Seisaku-Sho, Ltd.). Details of the
method for measuring the melt viscosity are described in Examples
later.
The polycarbonate resin (A) preferably contains a catalyst
deactivator. The catalyst deactivator is not particularly limited
as long as it is an acidic substance and has a function of
deactivating the polymerization catalyst, and the catalyst
deactivator includes, for example, phosphoric acid; trimethyl
phosphate; triethyl phosphate; phosphorous acid; a phosphonium salt
such as tetrabutylphosphonium octylsulfonate,
tetramethylphosphonium benzenesulfonate, tetrabutylphosphonium
benzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate and
tetrabutylphosphonium P-toluenesulfonate; an ammonium salt such as
tetramethylammonium decylsulfonate and tetrabutylammonium
dodecylbenzenesulfonate; and an alkyl ester such as methyl
benzenesulfonate, butyl benzenesulfonate, methyl
p-toluenesulfonate, butyl p-toluenesulfonate and ethyl
hexadecylsulfonate.
The catalyst deactivator preferably contains a phosphorus-based
compound containing a partial structure represented by either the
following structural formula (5) or structural formula (6)
(hereinafter, referred to as "specific phosphorus-based compound").
The specific phosphorus-based compound can deactivate the
later-described polymerization catalyst by its addition after the
completion of polycondensation reaction, i.e., for example, in the
kneading step or pelletizing step, and prevent the polycondensation
reaction from uselessly proceeding after that. As a result, the
progress of polycondensation upon heating of the polycarbonate
resin (A) in the molding step, etc. can be inhibited and in turn,
desorption of the monohydroxy compound can be suppressed.
Furthermore, coloring of the polycarbonate resin (A) under high
temperature can be more successfully suppressed by deactivating the
polymerization catalyst.
##STR00008##
As the specific phosphorus-based compound containing a partial
structure represented by structural formula (5) or (6), a
phosphoric acid, a phosphorous acid, a phosphonic acid, a
hypophosphorous acid, a polyphosphoric acid, a phosphonic acid
ester, an acidic phosphoric acid ester, etc. can be employed. Among
specific phosphorus-based compounds, a phosphorous acid, a
phosphonic acid, and a phosphonic acid ester are more excellent in
the effect of deactivating the catalyst or inhibiting the coloring,
and a phosphorous acid is particularly preferred.
As the phosphonic acid, for example, the following compounds can be
employed: phosphonic acid (phosphorous acid), methylphosphonic
acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic
acid, phenylphosphonic acid, benzylphosphonic acid,
aminomethylphosphonic acid, methylenediphosphonic acid,
1-hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic
acid, nitrilotris(methylenephosphonic acid), propylphosphonic
anhydride, etc.
As the phosphonic acid ester, for example, the following compounds
can be employed: dimethyl phosphonate, diethyl phosphonate,
bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl
phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl
methylphosphonate, diphenyl methylphosphonate, diethyl
ethylphosphonate, diethyl benzylphosphonate, dimethyl
phenylphosphonate, diethyl phenylphosphonate, dipropyl
phenylphosphonate, diethyl (methoxymethyl)phosphonate, diethyl
vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl
(2-hydroxyethyl)phosphonate, diethyl p-methylbenzylphosphonate,
diethylphosphonoacetic acid, ethyl diethylphosphonoacetate,
tert-butyl diethylphosphonoacetate, diethyl
(4-chlorobenzyl)phosphonate, diethyl cyanophosphonate, diethyl
cyanomethylphosphonate, diethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethylphosphonoacetaldehyde diethylacetal, diethyl
(methylthiomethyl)phosphonate, etc.
As the acidic phosphoric acid ester, for example, the following
compounds can be employed: a phosphoric acid diester such as
dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl
phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate,
bis(2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl
phosphate, distearyl phosphate, diphenyl phosphate and dibenzyl
phosphate, a mixture of phosphoric acid diester/monoester, diethyl
chlorophosphate, zinc stearyl phosphate, etc.
One of these specific phosphorus-based compounds may be used alone,
or two or more thereof may be mixed and used in arbitrary
combination and ratio.
The content of the specific phosphorus-based compound in the
polycarbonate resin (A) is preferably from 0.1 to 5 ppm by weight
in terms of phosphorus atom. In this case, the effect of the
specific phosphorus-based compound of deactivating the catalyst or
inhibiting the coloring can be satisfactorily obtained.
Furthermore, in this case, coloring of the polycarbonate resin (A)
can be more successfully prevented particularly in an endurance
test at high temperature and high humidity.
In addition, the effect of deactivating the catalyst or inhibiting
the coloring can be more reliably obtained by adjusting the content
of the specific phosphorus-based compound according to the amount
of the polymerization catalyst. The content of the specific
phosphorus-based compound is, in terms of phosphorus atom,
preferably from 0.5 to 5 times by mol, more preferably from 0.7 to
4 times by mol, still more preferably from 0.8 to 3 times by mol,
per mol of metal atoms in the polymerization catalyst.
Incidentally, the content of the acidic compound (E) in the
polycarbonate resin composition can be measured as the amount of
elements contained in the acidic compound (E) by means of ICP-MS
(inductively coupled plasma mass spectrometer).
[Aromatic Polycarbonate Resin (B)]
The aromatic polycarbonate resin (B) includes, for example, a
polycarbonate resin containing, as a main constitutional unit, a
constitutional unit derived from an aromatic dihydroxy compound
represented by the following formula (7):
##STR00009##
In formula (7), each of R.sup.1 to R.sup.8 independently represents
a hydrogen atom or a substituent. Y represents a single bond or a
divalent group. The substituent of R.sup.1 to R.sup.8 in formula
(7) is an alkyl group having a carbon number of 1 to 10, which may
have a substituent, an alkoxy group having a carbon number of 1 to
10, which may have a substituent, a halogen group, an alkyl halide
group having a carbon number of 1 to 10, or an aromatic group
having a carbon number of 6 to 20, which may have a substituent.
Among these, an alkyl group having a carbon number of 1 to 10,
which may have a substituent, or an aromatic group having a carbon
number of 6 to 20, which may have a substituent, is preferred. The
divalent group of Y in formula (7) includes an alkylene group
having a chain structure with a carbon number of 1 to 6, which may
have a substituent, an alkylidene group having a chain structure
with a carbon number of I to 6, which may have a substituent, an
alkylene group having a cyclic structure with a carbon number of 3
to 6, which may have a substituent, an alkylidene group having a
cyclic structure with a carbon number of 3 to 6, which may have a
substituent, --O--, --S--, --CO--, and --SO.sub.2--. Here, although
the substituent is not particularly limited as long as it does not
inhibit the effects of the present invention, the substituent is
usually a substituent having a molecular weight of 200 or less. The
substituent on an alkylene group having a chain structure with a
carbon number of 1 to 6 is preferably an aryl group, more
preferably a phenyl group.
Although the aromatic polycarbonate resin (B) may be either a
homopolymer or a copolymer, in the case of a copolymer, the resin
is preferably a polycarbonate resin where a constitutional unit
derived from an aromatic dihydroxy compound represented by formula
(7) accounts for a largest proportion among all constitutional
units derived from a dihydroxy compound. In the aromatic
polycarbonate resin (B), the content ratio of the constitutional
unit derived from an aromatic dihydroxy compound represented by
formula (7), relative to 100 mol % of all constitutional units
derived from all dihydroxy compounds, is preferably 50 mol % or
more, more preferably 70 mol % or more, still more preferably 90
mol % or more.
The aromatic polycarbonate resin (B) may have either a branched
structure or a linear structure or may have a mixture of a branched
structure and a linear structure. Furthermore, the aromatic
polycarbonate resin (B) may be a resin containing a constitutional
unit derived from a dihydroxy compound having a moiety represented
by formula (1). However, in the case of a resin containing a
constitutional unit derived from a dihydroxy compound having a
moiety represented by formula (1), a polycarbonate resin having a
constitutional unit different from that of the polycarbonate resin
(A) is used.
The dihydroxy compound-derived constitutional unit constituting the
aromatic polycarbonate resin (B) is formed by removing a hydrogen
atom from a hydroxyl group of a dihydroxy compound. Specific
examples of the corresponding dihydroxy compound include the
followings:
a biphenyl compound such as 4,4'-biphenol, 2,4'-biphenol,
3,3'-dimethyl-4,4'-dihydroxy-1,1'-biphenyl,
3,3'-dimethyl-2,4'-dihydroxy-1,1'-biphenyl,
3,3'-di-(tert-butyl)-4,4'-dihydroxy-1,1'-biphenyl,
3,3',5,5'-tetramethyl-4,4'-dihydroxy-1,1'-biphenyl,
3,3',5,5'-tetra-(tert-butyl)-4,4'-dihydroxy-1,1'-biphenyl, and
2,2',3,3',5,5'-hexamethyl-4,4'-dihydroxy-1,1'-biphenyl;
a bisphenol compound such as
bis-(4-hydroxy-3,5-dimethylphenyl)methane,
bis-(4-hydroxyphenyl)methane,
bis-(4-hydroxy-3-methylphenyl)methane,
1,1-bis-(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxy-3-methylphenyl)propane,
2,2-bis-(4-hydroxyphenyl)butane, 2,2-bis-(4-hydroxyphenyl)pentane,
2,2-bis-(4-hydroxyphenyl)-3-methylbutane,
2,2-bis-(4-hydroxyphenyl)hexane,
2,2-bis-(4-hydroxyphenyl)-4-methylpentane,
1,1-bis-(4-hydroxyphenyl)cyclopentane,
1,1-bis-(4-hydroxyphenyl)cyclohexane,
bis-(3-phenyl-4-hydroxyphenyl)methane,
1,1-bis-(3-phenyl-4-hydroxyphenyl)ethane,
1,1-bis-(3-phenyl-4-hydroxyphenyl)propane,
2,2-bis-(3-phenyl-4-hydroxyphenyl)propane,
1,1-bis-(4-hydroxy-3-methylphenyl)ethane,
2,2-bis-(4-hydroxy-3-ethylphenyl)propane,
2,2-bis-(4-hydroxy-3-isopropylphenyl)propane,
2,2-bis-(4-hydroxy-3-sec-butylphenyl)propane,
1,1-bis-(4-hydroxy-3,5-dimethylphenyl)ethane,
2,2-bis-(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis-(4-hydroxy-3, 6-dimethylphenyl)ethane,
bis-(4-hydroxy-2,3,5-trimethylphenyl)methane,
1,1-bis-(4-hydroxy-2,3,5-trimethylphenyl)ethane,
2,2-bis-(4-hydroxy-2,3,5-trimethylphenyl)propane,
bis-(4-hydroxy-2,3,5-trimethylphenyl)phenylmethane,
1,1-bis-(4-hydroxy-2,3,5-trimethylphenyl)phenylethane,
1,1-bis-(4-hydroxy-3,3,5-trimethylphenyl)cyclohexane,
bis-(4-hydroxyphenyl)phenylmethane,
1,1-bis-(4-hydroxyphenyl)-1-phenylethane,
1,1-bis-(4-hydroxyphenyl)-1-phenylpropane,
bis-(4-hydroxyphenyl)diphenylmethane,
bis-(4-hydroxyphenyl)dibenzylmethane,
4,4'-[1,4-phenylenebis(1-methylethylidene)]bis-[phenol],
4,4'-[1,4-phenylenebismethylene]bis-[phenol],
4,4'-[1,4-phenylenebis(1-methylethylidene)]bis-[2,6-dimethylphenol],
4,4'-[1,4-phenylenebismethylene]bis-[2,6-dimethylphenol],
4,4'-[1,4-phenylenebismethylene]bis-[2,3,6-trimethylphenol],
4,4'-[1,4-phenylenebis(1-methylethylidene)]bis-[2,3,6-trimethylphenol],
4,4'-[1,3-phenylenebis(1-methylethylidene)]bis-[2,3,6-trimethylphenol],
4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone,
4,4'-dihydroxydiphenyl sulfide,
3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl ether,
3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylsulfone,
3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide
phenolphthalein,
4,4'-[1,4-phenylenebis(1-methylvinylidene)]bisphenol,
4,4'-[1,4-phenylenebis(1-methylvinylidene)]bis[2-methylphenol],
(2-hydroxyphenyl)(4-hydroxyphenyl)methane,
(2-hydroxy-5-methylphenyl)(4-hydroxy-3-methylphenyl)methane,
1,1-(2-hydroxyphenyl)(4-hydroxyphenyl)ethane,
2,2-(2-hydroxyphenyl)(4-hydroxyphenyl)propane, and
1,1-(2-hydroxyphenyl)(4-hydroxyphenyl)propane; and
a halogenated bisphenol compound such as
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane.
Among these dihydroxy compounds, preferred are
bis-(4-hydroxy-3,5-dimethylphenyl)methane,
bis-(4-hydroxyphenyl)methane,
bis-(4-hydroxy-3-methylphenyl)methane,
1,1-bis-(4-hydroxyphenyl)ethane, 2,2-bis-(4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxy-3-methylphenyl)propane,
2,2-bis-(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis-(4-hydroxyphenyl)cyclohexane,
1,1-bis-(4-hydroxy-3,3,5-trimethylphenyl)cyclohexane,
bis-(4-hydroxyphenyl)phenylmethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
1,1-bis(4-hydroxyphenyl)-1-phenylpropane,
bis(4-hydroxyphenyl)diphenylmethane,
2-hydroxyphenyl(4-hydroxyphenyl)methane, and
2,2-(2-hydroxyphenyl)(4-hydroxyphenyl)propane.
Among these, more preferred are bis-(4-hydroxyphenyl)methane,
bis-(4-hydroxy-3-methylphenyl)methane,
bis-(4-hydroxy-3,5-dimethylphenyl)methane,
2,2-bis-(4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxy-3-methylphenyl)propane,
2,2-bis-(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis-(4-hydroxyphenyl)cyclohexane, and
1,1-bis-(4-hydroxy-3,3,5-trimethylphenyl)cyclohexane.
As for the production method of the aromatic polycarbonate resin
(B), any conventionally known method, such as phosgene method,
transesterification method or pyridine method, may be used. As an
example, a method for producing the aromatic polycarbonate resin
(B) by a transesterification process is described below.
The transesterification process is a production method of
performing melt transesterification and polycondensation by adding
a dihydroxy compound, a carbonic acid diester and a basic catalyst
and by further adding an acidic substance for neutralizing the
basic catalyst. The dihydroxy compound includes the biphenyl
compounds and bisphenol compounds recited above as examples.
Representative examples of the carbonic acid diester include
diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate,
m-cresyl carbonate, dinaphthyl carbonate, bis(biphenyl) carbonate,
diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and
dicyclohexyl carbonate. Among these, diphenyl carbonate is
preferably used.
In view of the balance between mechanical properties and
moldability, the viscosity average molecular weight of the aromatic
polycarbonate resin (B) is usually from 8,000 to 30,000, preferably
from 10,000 to 25,000. As for the reduced viscosity of the aromatic
polycarbonate resin (B), a solution prepared by using methylene
chloride as a solvent and precisely adjusting the polycarbonate
concentration to 0.60 g/dL is measured at a temperature of
20.0.+-.0.1.degree. C. The reduced viscosity is usually from 0.23
to 0.72 dL/g, and preferably from 0.27 to 0.61 dL/g.
In the present invention, only one of these aromatic polycarbonate
resins (B) may be used alone, or two or more thereof may be mixed
and used.
[Compound (C)]
The compound (C) blended in the polycarbonate resin composition can
promote the transesterification reaction of the polycarbonate resin
(A) with the aromatic polycarbonate resin (B). The
transesterification reaction occurs due to heating at the time of
manufacturing the resin composition, for example, when kneading the
polycarbonate resin (A) and the aromatic polycarbonate resin (B),
and is promoted by the compound (C). As a result, compatibility
between the polycarbonate resin (A) and the aromatic polycarbonate
resin (B) in the resin composition is enhanced and therefore, the
transparency of the resin composition can be increased. In turn, a
resin composition having excellent properties such as heat
resistance, wet heat resistance and impact resistance can be
realized while providing high transparency without decreasing the
biogenic substance content rate. The compound (C) may be a compound
containing at least one member selected from Group 1 metals and
Group 2 metals of the long-form periodic table, and it is
preferable to contain a compound of a Group 1 metal of the
long-form periodic table, because the haze is low and the wet heat
resistance and heat resistance are improved.
In particular, as described later, it is preferred that at least a
compound of a Group 1 metal of the long-form periodic table is
contained as the compound (C) and the content of the compound of a
Group 1 metal of the long-form periodic table per 100 parts by
weight of the total amount of the polycarbonate resin (A) and the
aromatic polycarbonate resin (B) is from 0.8 to 1,000 ppm by
weight, because lower haze and higher wet heat resistance and heat
resistance are achieved and good color tone, wet heat resistance
and transparency can be more enhanced.
Examples of the metal in the compound (C) include lithium, sodium,
potassium, rubidium, cesium, beryllium, magnesium, calcium,
strontium, and barium.
Among the Group 1 and Group 2 metals, the metal in the compound (C)
is preferably a metal having an electronegativity of 0.7 to 1.1,
more preferably a metal having an electronegativity of 0.75 to 1.0,
and still more preferably a metal having an electronegativity of
0.75 to 0.98. Specifically, such a metal includes cesium (0.79),
potassium (0.82), sodium (0.93), lithium (0.98), barium (0.89),
strontium (0.95), and calcium (1.0). The numerical value in the
parenthesis is the electronegativity. When the electronegativity is
in the range above, it is presumed that the nucleophilicity of a
counter ion increases and the transesterification reaction of the
polycarbonate resin (A) with the aromatic polycarbonate resin (B)
can thereby be more promoted. Accordingly, by employing a metal
with an electronegativity in the range above, the transparency of
the polycarbonate resin composition can be more enhanced, and the
impact resistance can be more increased.
The compound (C) includes an inorganic salt (including a
carbonate), a carboxylate, a phenolate, a halogen compound, and a
hydroxylated compound, and at least one member selected from these
compounds can be used. Specifically, the compound includes a metal
salt composed of the metal above and an active hydrogen-containing
compound, for example, an organic acid such as carboxylic acid,
carbonic acid and phenol, an inorganic acid such as nitric acid,
phosphoric acid, boric acid and silicic acid, an alcohol, a thiol,
or a primary or secondary amine. The active hydrogen-containing
compound may contain a plurality of active hydrogens of the same
functional group per molecule or may have two or more functional
groups per molecule. It is presumed that such a compound has good
dispersibility in the polycarbonate resin (A) or aromatic
polycarbonate resin (B) and the transesterification reaction of the
polycarbonate resin (A) with the aromatic polycarbonate resin (B)
can thereby be more promoted. Among these, a metal salt with an
organic acid such as carboxylic acid, carbonic acid or phenol or
with an inorganic acid consisting of nitric acid, phosphoric acid,
boric acid, etc. is preferred, and a metal salt with an organic
acid such as carboxylic acid or carbonic acid or with an inorganic
acid consisting of nitric acid, phosphoric acid, boric acid, etc.
is more preferred. The metal salt includes halide of the metal and
hydroxide of the metal.
The acid dissociation constant (pKa) of the counter ion to the
metal ion in the compound (C) is preferably from 2 to 16. In this
case, the transparency of the polycarbonate resin composition can
be enhanced without increasing the amount of catalyst in terms of
metal, and deterioration of the color hue can be more successfully
prevented. From the same viewpoint, the acid dissociation constant
(pKa) of the counter ion to the metal ion in the compound (C) is
more preferably from 3 to 11, and still more preferably from 5 to
10.
As the Group 1 metal compound used as the compound (C), for
example, the following compounds can be employed: sodium hydroxide,
potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium
hydrogencarbonate, potassium hydrogencarbonate, lithium
hydrogencarbonate, cesium hydrogencarbonate, sodium carbonate,
potassium carbonate, lithium carbonate, cesium carbonate, sodium
acetate, potassium acetate, lithium acetate, cesium acetate, sodium
stearate, potassium stearate, lithium stearate, cesium stearate,
sodium borohydride, potassium borohydride, lithium borohydride,
cesium borohydride, sodium borophenylate, potassium borophenylate,
lithium borophenylate, cesium borophenylate, sodium benzoate,
potassium benzoate, lithium benzoate, cesium benzoate, disodium
hydrogenphosphate, dipotassium hydrogenphosphate, dilithium
hydrogenphosphate, dicesium hydrogenphosphate, disodium
phenylphosphate, dipotassium phenylphosphate, dilithium
phenylphosphate, dicesium phenylphosphate, an alcoholate or
phenolate of sodium, potassium, lithium and cesium, disodium,
dipotassium, dilithium and dicesium salts of bisphenol A, etc.
Among these, from the viewpoint of more enhancing the color hue,
impact resistance and reactivity, at least one member selected from
the group consisting of a lithium compound, a sodium compound, a
potassium compound and a cesium compound is preferred. It is
presumed that such a compound has an electronegativity in a proper
range and can more promote the transesterification reaction of the
polycarbonate resin (A) with the aromatic polycarbonate resin (B).
Furthermore, from the viewpoint of more enhancing the transparency,
color tone and wet heat resistance, at least one member selected
from the group consisting of a sodium compound, a potassium
compound and a cesium compound is preferred; a potassium compound
and/or a cesium compound is more preferred; and potassium
hydrogencarbonate, cesium hydrogencarbonate, potassium carbonate,
cesium carbonate, potassium acetate, cesium acetate, potassium
stearate, and cesium stearate are still more preferred.
As the Group 2 metal compound used as the compound (C), for
example, the following compounds can be employed: calcium
hydroxide, barium hydroxide, magnesium hydroxide, strontium
hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate,
magnesium hydrogencarbonate, strontium hydrogencarbonate, calcium
carbonate, barium carbonate, magnesium carbonate, strontium
carbonate, calcium acetate, barium acetate, magnesium acetate,
strontium acetate, calcium stearate, barium stearate, magnesium
stearate, strontium stearate, etc. Among these, from the viewpoint
of more enhancing the transparency and color tone, a calcium
compound is preferred, and calcium hydroxide, calcium
hydrogencarbonate and calcium acetate are more preferred.
The amount of metal derived from the compound (C) contained in the
polycarbonate resin composition is from 0.8 to 1,000 ppm by weight
per 100 parts by weight of the total amount of the polycarbonate
resin (A) and the aromatic polycarbonate resin (B). Although it may
vary depending on the metal species, if the metal amount exceeds
1,000 ppm by weight, the color tone of the resin composition
deteriorates and the wet heat resistance lowers. If the metal
amount is less than 0.8 ppm by weight, the transparency of the
resin composition is insufficient. From the viewpoint of more
enhancing the color tone, wet heat resistance and transparency, the
amount of metal derived from the compound (C) is more preferably
from 0.9 to 100 ppm by weight, and still more preferably from 1 to
10 ppm by weight. Incidentally, in general, the compound (C)
introduced into the polycarbonate resin composition is often
deactivated, for example, after the polymerization step by an
acidic compound such as butyl p-toluenesulfonate, rather than by
the polymerization catalyst for the polycarbonate resin (A) as a
raw material or the polymerization catalyst for the aromatic
polycarbonate resin (B), and it is therefore preferable to add the
compound (C) separately as described later. The compound (C)
contained in the polycarbonate resin composition is a concept
encompassing both a polymerization catalyst corresponding to the
compound (C) used at the time of production of the polycarbonate
resin (A) and the aromatic polycarbonate resin (B) and introduced
into the resin composition from each of the resin (A) and the resin
(B), and a compound (C) added separately at the time of manufacture
of the resin composition.
Accordingly, the resin composition of the present invention
preferably contains a compound of a Group I metal of the long-form
periodic table and a compound of a Group 2 metal of the long-form
periodic table, because low haze and good wet heat resistance and
heat resistance are achieved and color tone, wet heat resistance
and transparency can be more enhanced.
Here, the content of the compound (C) in the polycarbonate resin
composition can be measured as a metal amount by using ICP-MS
(inductively coupled plasma mass spectrometer).
The amount of the compound (C) added at the time of production of
the resin composition may vary depending on the metal species and
is, in terms of metal, from 0.5 to 1,000 ppm by weight, preferably
from 1 to 100 ppm by weight, more preferably from 1 to 10 ppm by
weight, per 100 parts by weight of the total amount of the
polycarbonate resin (A) and the aromatic polycarbonate resin (B).
If the amount added is less than 0.5 ppm by weight, the
transparency of the resin composition is insufficient. On the other
hand, if the amount added exceeds 1,000 ppm by weight, the resin
composition may be transparent but is intensely colored and in
addition, the molecular weight (melt viscosity) thereof is reduced,
failing in obtaining a resin composition with excellent impact
resistance.
As for the method of adding the compound (C), a compound that is
solid may be supplied as a solid, or a compound capable of
dissolving in water or a solvent may be added in the form of an
aqueous solution or a solution. The compound may be added to the
polycarbonate resin raw material or in the case of an aqueous
solution or a solution, may be charged from a raw material charging
port of an extrude or liquid-added from a cylinder by means of a
pump, etc.
[Crown Ether Compound (D)]
As the crown ether compound (D) (hereinafter, sometimes
appropriately referred to as "compound (D)") for use in the present
invention, an arbitrary compound may be selected, according to the
purpose, from various compounds generally known as a crown ether.
Crown ethers having a simplest structure are represented by the
formula (--CH.sub.2--CH.sub.2--O--).sub.n. Out of these crown
ethers, crown ethers of the formula where n is 4 to 7 are preferred
in the present invention. The crown ether is sometimes referred to
as an "x-crown-y-ether" in which x is the total number of atoms
constituting the ring and y is the number of oxygen atoms contained
therein. In the present invention, at least one member selected
from the group consisting of crown ethers of x=12, 15, 18 and 21
and y=x/3, benzo-condensed products thereof, and
cyclohexyl-condensed products thereof is preferably used. More
preferred specific examples of the crown ether include
21-crown-7-ether, 18-crown-6-ether, 15-crown-5-ether,
12-crown-4-ether, dibenzo-21-crown-7-ether,
dibenzo-18-crown-6-ether, dibenzo-15-crown-5-ether,
dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether,
dicyclohexyl-18-crown-6-ether, dicyclohexyl-15-crown-5-ether, and
dicyclohexyl-12-crown-4-ether. Among these, it is most preferable
to select the compound from 18-crown-6-ether and
15-crown-5-ether.
The content of the compound (D) is from 0.1 to 10 times by mol
relative to the amount, in terms of metal, of the compound (C). If
the content is less than 0.1 times by mol, the effect of reducing
the amount added of the compound (C) due to addition of the
compound (D) is insufficient. As a result, the transparency of the
resin composition may be impaired. On the other hand, if the
content exceeds 10 times by mol, the resin composition may be
intensely colored, though the transparency can be enhanced.
Furthermore, the molecular weight (melt viscosity) of the resin
composition is reduced, and the impact resistance may be
insufficient. From the viewpoint of more enhancing the transparency
and impact resistance and more suppressing the coloring, the
content of the compound (D) is preferably from 0.5 to 5 times by
mol, more preferably from 0.7 to 4 times by mol, still more
preferably from 1 to 3 times by mol, relative to the amount, in
terms of metal, of the compound (C).
As for the method of adding the compound (D), a compound that is
solid may be supplied as a solid, or a compound capable of
dissolving in water or a solvent may be added in the form of an
aqueous solution or a solution. The compound may be added to the
polycarbonate resin raw material or in the case of an aqueous
solution or a solution, may be charged from a raw material charging
port of an extrude or liquid-added from a cylinder by means of a
pump, etc.
Incidentally, the crown ether compound can be detected, for
example, as follows.
That is, the crown ether compound can be detected by gas
chromatograph-mass spectrometry after dissolving the polymer in a
solvent such as methylene chloride, precipitating the polymer by
using acetone, etc., and collecting the acetone.
[Acidic Compound (E)]
The polycarbonate resin composition preferably further contains an
acidic compound (E). The acidic compound (E) is added at the time
of blending of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) and is a concept not encompassing the
above-described catalyst deactivator used when producing the
polycarbonate resin (A) and the aromatic polycarbonate resin (B).
Because, the catalyst deactivator has deprived of the effect itself
in the stage of production of the polycarbonate resin (A) and the
aromatic polycarbonate resin (B). Here, as the acidic compound (E),
the same substances as those for the above-described catalyst
deactivator can be used.
The content of the acidic compound (E) is preferably from 0.1 to 5
times by mol per mol of the content of metal in the compound (C)
contained in the polycarbonate resin composition. In this case, the
wet heat resistance can be more enhanced and at the same time, the
thermal stability, for example, during molding can be more
increased. From the same viewpoint, the content of the acidic
compound (E) is preferably from 0.5 to 2 times by mol, more
preferably from 0.6 to 1.5 times by mol, and most preferably from
0.7 to 1 times by mol, per mol of the content of metal in the
compound (C).
Here, the content of the acidic compound (E) in the polycarbonate
resin composition can be measured as the amount of elements
contained in the acidic compound (E) by using ICP-MS (inductively
coupled plasma mass spectrometer).
[Polycarbonate Resin Composition]
In the polycarbonate resin composition of the present invention,
the total light transmittance in the thickness direction of a
molded body having a thickness of 2 mm obtained by molding the
resin composition is preferably 80% or more. From the viewpoint
that the applicability to transparent usage and the image clarity
at the time of spin-dyeing are improved, the total light
transmittance is more preferably 85% or more, still more preferably
88% or more, and yet still more preferably 90% or more. The haze of
a molded body having a thickness of 2 mm is preferably 1% or less,
more preferably 0.5% or less, still more preferably 0.3% or less.
The method for measuring the total light transmittance is described
later in Examples. The haze can also be measured by the same method
as that for the total light transmittance.
In the polycarbonate resin composition, the peak of the glass
transition temperature as measured by the DSC method (differential
scanning calorimetry) is preferably single.
In the present invention, the glass transition temperature of the
polycarbonate resin composition is single, and this specifically
means that when the glass transition temperature of the
polycarbonate resin composition is measured using a differential
scanning calorimeter (DSC) by the following method, only one
inflection point indicating the glass transition temperature
appears. Due to the single glass transition temperature of the
polycarbonate resin composition, the obtained molded body can
realize excellent transparency.
(Measurement of Glass Transition Temperature)
Tg of the polycarbonate resin composition is defined as a value of
Tmg determined in conformity with the method of JIS-K7121 (1987)
from a DSC curve obtained by using a differential scanning
calorimeter, "DSC7", manufactured by Perkin Elmer, Inc. and
subjecting the resin composition, in a nitrogen gas atmosphere, to
temperature rise to 200.degree. C. from 25.degree. C. at a heating
rate of 20.degree. C./min; holding at 200.degree. C. for 3 minutes;
temperature drop to 25.degree. C. at a cooling rate of 20.degree.
C./min; holding at 25.degree. C. for 3 minutes; and again
temperature rise to 200.degree. C. at a heating rate of 5.degree.
C./min. As for the evaluation of singularity in the glass
transition temperature, specifically, when the peak of the DSC
curve is single (i.e., only one inflection point indicating the
glass transition temperature appears), the glass transition
temperature is judged as being single, and when the DSC curve has a
plurality of peaks (i.e., a plurality of inflections points
indicating the glass transition temperature appear), the glass
transition temperature is judged as not being single.
In general, a single glass transition temperature of a polymer
blend composition means that the resins mixed are in the state of
being compatibilized in nanometer order (molecular level), and this
can be recognized as a compatibilized system.
The glass transition temperature of the polycarbonate resin
composition is preferably from 100 to 200.degree. C. In this case,
the heat resistance can be more enhanced and in turn, deformation
of a molded article can be more successfully prevented. In
addition, in this case, thermal degradation of the polycarbonate
resin (A) at the time of production of the resin composition can be
still more successfully prevented, and the impact resistance can be
more enhanced. Furthermore, thermal degradation of the resin
composition during molding can be more suppressed. From the same
viewpoint, the glass transition temperature of the polycarbonate
resin composition is more preferably from 110 to 190.degree. C.,
and still more preferably from 120 to 180.degree. C.
A polycarbonate resin composition exhibiting the above-described
predetermined total light transmittance and glass transition
temperature can be realized by including a polycarbonate resin (A)
containing a constitutional unit derived from a compound
represented by formula (1), an aromatic polycarbonate resin (B),
and the above-described specific compound (C), and adjusting the
content of the compound (C) to fall in the predetermined range
above.
Alternatively, a polycarbonate resin composition exhibiting the
above-described predetermined total light transmittance and glass
transition temperature can be realized by including a polycarbonate
resin (A) containing a constitutional unit derived from a compound
represented by formula (1), an aromatic polycarbonate resin (B),
the above-described specific compound (C), and the above-described
specific compound (D), and adjusting the content of the compound
(C) and the content of the compound (D) to fall in the
predetermined ranges above.
The blending ratio of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) in the polycarbonate resin composition can
be arbitrarily selected according to the desired physical
properties. From the viewpoint of more increasing the biogenic
substance content rate, the weight ratio (A/B) of the polycarbonate
resin (A) and the aromatic polycarbonate resin (B) is preferably
from 95/5 to 50/50, and more preferably from 90/10 to 60/40. With a
weight ratio in this range, the heat resistance, impact resistance
and biogenic substance content rate can be increased in a better
balanced manner.
Assuming that the sum of the melt viscosity of the polycarbonate
resin (A) and the melt viscosity of the aromatic polycarbonate
resin (B) each multiplied by the weight ratio is the ideal melt
viscosity, the melt viscosity of the polycarbonate resin
composition is preferably 40% or more relative to the ideal melt
viscosity. In this case, the impact strength can be more enhanced.
From the same viewpoint, the melt viscosity of the polycarbonate
resin composition is more preferably 60% or more, still more
preferably 80% or more, relative to the ideal melt viscosity. Here,
the melt viscosity indicates a melt viscosity at a temperature of
240.degree. C. and a shear rate of 91.2 sec.sup.-1 as measured by
using a capillary rheometer [manufactured by Toyo Seiki
Seisaku-Sho, Ltd.). Details of the method for measuring the melt
viscosity are described in Examples later.
[Other Additives]
In the polycarbonate resin composition, various additives can be
added. The additive includes a dye/pigment, an antioxidant, a UV
absorber, a light stabilizer, a release agent, a heat stabilizer, a
flame retardant, a flame retardant aid, an inorganic filler, an
impact improver, a hydrolysis inhibitor, a foaming agent, a
nucleating agent, etc., and an additive that is usually used for a
polycarbonate resin can be used.
[Dye/Pigment]
The dye/pigment includes an inorganic pigment and an organic
dye/pigment such as organic pigment and organic dye.
The inorganic pigment specifically includes, for example, carbon
black; and an oxide-based pigment such as titanium oxide, zinc
oxide, red oxide, chromium oxide, iron black, titanium yellow,
zinc-iron brown, copper-chromium black and copper-iron black.
The organic dye/pigment such as organic pigment and organic dye
specifically includes, for example, a phthalocyanine-based
dye/pigment; a condensed polycyclic dye/pigment such as azo type,
thioindigo type, perinone type, perylene type, quinacridone type,
dioxazine type, isoindolinone type and quinophthalone type; and
anthraquinone-based, perinone-based, perylene-based, methine-based,
quinoline-based, heterocyclic and methyl-based dyes/pigments.
One of these dyes/pigments may be used alone, or two or more
thereof may be mixed and used.
Among these inorganic pigments and organic dyes/pigments such as
organic pigment and organic dye, an inorganic pigment is preferred.
By using an inorganic pigment as a coloring agent, even when a
molded article is used outdoors, etc., for example, the image
clarity is little degraded and can be held for a long period of
time.
The amount of the dye/pigment is preferably from 0.05 to 5 parts by
weight, more preferably from 0.05 to 3 parts by weight, and still
more preferably from 0.1 to 2 parts by weight, per 100 parts by
weight of the total of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B). If the amount of the coloring agent is
less than 0.05 parts by weight, a spun-dyed molded article with
high image clarity can be hardly obtained. If the amount exceeds 5
parts by weight, the surface roughness of a molded article is
increased, and a spun-dyed molded article with high image clarity
can be hardly obtained.
[Antioxidant]
As the antioxidant, a general antioxidant used for a resin can be
used, and in view of oxidation stability and thermal stability, a
phosphite-based antioxidant, a sulfur-based antioxidant, and a
phenolic antioxidant are preferred. The amount of the antioxidant
added is preferably 5 parts by weight or less per 100 parts by
weight of the total of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B). In this case, contamination of the mold
during molding can be more reliably prevented, and a molded article
with more excellent surface appearance can be obtained. From the
same viewpoint, the amount of the antioxidant added is more
preferably 3 parts by weight or less, still more preferably 2 parts
by weight or less, per 100 parts by weight of the total of the
polycarbonate resin (A) and the aromatic polycarbonate resin (B).
In addition, the amount of the antioxidant added is preferably
0.001 parts by weight or more per 100 parts by weight of the total
of the polycarbonate resin (A) and the aromatic polycarbonate resin
(B). In this case, the effect of improving the molding stability
can be sufficiently obtained. From the same viewpoint, the amount
of the antioxidant added is more preferably 0.002 parts by weight
or more, still more preferably 0.005 parts by weight or more, per
100 parts by weight of the total of the polycarbonate resin (A) and
the aromatic polycarbonate resin (B).
(Phosphite-Based Antioxidant)
The phosphite-based antioxidant includes triphenyl phosphite,
tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite,
tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite,
didecylmonophenyl phosphite, dioctylmonophenyl phosphite,
diisopropylmonophenyl phosphite, monobutyldiphenyl phosphite,
monodecyldiphenyl phosphite, monooctyldiphenyl phosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite,
bis(nonylphenyl)pentaerythritol diphosphite,
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,
distearylpentaerythritol diphosphite, etc.
Among these, trisnonylphenyl phosphite,
tris(2,4-di-tert-butylphenyl)phosphite,
bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite
are preferably used. One of these compounds may be used, or two or
more thereof may be used in combination.
(Sulfur-Based Antioxidant)
The sulfur-based antioxidant includes, for example,
dilauryl-3,3'-thiodipropionic acid ester,
ditridecyl-3,3'-thiodipropionic acid ester,
dimyristyl-3,3'-thiodipropionic acid ester,
distearyl-3,3'-thiodipropionic acid ester,
laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol
tetrakis(3-laurylthiopropionate),
bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]
sulfide, octadecyl disulfide, mercaptobenzimidazole,
2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol).
Among these, pentaerythritol tetrakis(3-laurylthiopropionate) is
preferred. One of these compounds may be used, or two or more
thereof may be used in combination.
(Phenolic Antioxidant)
The phenolic antioxidant includes, for example, compounds such as
pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol
tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate,
triethylene
glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]-
, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide),
diethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate,
3,9-bis{1,1-dimethyl-2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propiony-
loxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane,
2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol.
Among these compounds, an aromatic monohydroxy compound substituted
with one or more alkyl groups having a carbon number of 5 or more
is preferred. Specifically,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)-
,
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
etc. are preferred, and
pentaerythrityl-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}
is more preferred. One of these compounds may be used, or two or
more thereof may be used in combination.
[UV Absorber]
The ultraviolet absorber includes a benzotriazole-based compound, a
benzophenone-based compound, a triazine-based compound, a
benzoate-based compound, a hindered amine-based compound, a phenyl
salicylate-based compound, a cyanoacrylate-based compound, a
malonic acid ester-based compound, an oxalanilide-based compound,
etc. One of these may be used alone, or two or more thereof may be
used in combination.
More specific examples of the benzotriazole-based compound include
2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole,
2-(2'-hydroxy-3'-tert-butyl-5'-hexylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-3'-methyl-5'-tert-octylphenyl)benzotriazole,
2-(2'-hydroxy-5'-tert-dodecylphenyl)benzotriazole,
2-(2'-hydroxy-3'-methyl-5'-tert-dodecylphenyl)benzotriazole,
2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, and
methyl-3-[3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl]propiona-
te.
The triazine-based compound includes
2-{4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl}-4,
6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine,
2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin
1577FF, produced by BASF Japan), etc.
The hydroxybenzophenone-based compound includes
2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone,
2-hydroxy-4-octoxybenzophenone, etc.
The cyanoacrylate-based compound includes
ethyl-2-cyano-3,3-diphenyl acrylate,
2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, etc.
The malonic acid-ester-based compound includes 2-(1-aryl
alkylidene)malonic acid esters, etc. Among others,
[(4-methoxyphenyl)-methylene]-dimethyl malonate (Hostavin PR-25,
produced by Clariant), and dimethyl
2-(paramethoxybenzylidene)malonate are preferred.
The oxalanilide-based compound includes
2-ethyl-2'-ethoxy-oxalanilide (Sanduvor VSU, produced by Clariant),
etc.
Among these,
2-(2'-hydroxy-3'-tert-butyl-5'-hexylphenyl)benzotriazole,
2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole,
2-{4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl}-4,6-bis(2,4-dim-
ethylphenyl)-1,3,5-triazine, and 2,2',4,4'-tetrahydroxybenzophenone
are preferred.
[Light Stabilizer]
The light stabilizer includes a hindered amine-based stabilizer,
and the molecular weight thereof is preferably 1,000 or less. In
this case, the weather resistance of a molded article can be more
enhanced. From the same viewpoint, the molecular weight of the
light stabilizer is more preferably 900 or less. In addition, the
molecular weight of the light stabilizer is preferably 300 or more.
In this case, the heat resistance can be more enhanced, and
contamination of the mold during molding can be more reliably
prevented, as a result, a molded article with more excellent
surface appearance can be obtained. From the same viewpoint, the
molecular weight of the light stabilizer is more preferably 400 or
more. Furthermore, the light stabilizer is preferably a compound
having a piperidine structure. The piperidine structure as
prescribed herein may be sufficient if it takes on a saturated
6-membered cyclic amine structure, and the piperidine structure
also includes those in which part of the piperidine structure is
substituted with a substituent. The substituent includes an alkyl
group having a carbon number of 4 or less, and a methyl group is
particularly preferred. Among others, a compound having a plurality
of piperidine structures is preferred, and a compound in which the
plurality of piperidine structures are connected through an ester
structure is preferred.
Such a light stabilizer includes 4-piperidinol,
2,2,6,6-tetramethyl-4-benzoate,
bis(2,2,6,6-tetramethyl-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
tetrakis(2,2,6,6-tetramethylpiperidine-4-carboxylate)
1,2,3,4-butanetetrayl, a condensate of
2,2,6,6-tetramethyl-piperidinol with tridecyl alcohol and
1,2,3,4-butanetetracarboxylic acid, a condensate of
1,2,2,6,6-pentamethyl-4-piperidyl with tridecyl alcohol and
tridecyl-1,2,3,4-butanetetracarboxylate,
bis(1,2,3,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1-dimethylethyl)-4-hydr-
oxyphenyl]methyl}butyl malonate,
bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, a
reaction product of 1,1-dimethylethylhydroperoxide and octane,
1-{2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl
oxy]ethyl}-4-[3-(3,5-di-tert-butyl-4-4-hydroxyphenyl)propionyloxy]ethyl]--
2,2,6,6-tetramethylpiperidine,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate,
poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,
2,6, 6-tetramethyl-4-piperidyl)imino}hexamethylene
{(2,2,6,6-tetramethyl-4-piperidyl)imino}], a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexadiamine polymer
with 2,4,6-trichloro-1,3,5-triazine, a condensate of
1,2,3,4-butanetetracarboxylic acid with
2,2,6,6-tetramethyl-4-piperidinol and
.beta.,.beta.,.beta.,.beta.-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5-
,5]undecane-diethanol,
N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,
6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine
condensate, a dimethyl
succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperi-
dine polycondensate, etc.
The content of the light stabilizer is preferably from 0.001 to 5
parts by weight per 100 parts by weight of the total of the
polycarbonate resin (A) and the aromatic polycarbonate resin (B).
In this case, coloring of the polycarbonate resin composition can
be more successfully prevented. As a result, for example, when a
coloring agent is added, a deep and clear jet-black color can be
obtained. Furthermore, in this case, the light resistance of the
polycarbonate resin composition can be more enhanced, and for
example, even when the polycarbonate resin composition is applied
to automotive interior/exterior applications, excellent light
resistance can be exerted. The content of the light stabilizer is
more preferably from 0.005 to 3 parts by weight, still more
preferably from 0.01 to 1 part by weight, per 100 parts by weight
of the total of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B). Incidentally, the aromatic polycarbonate
resin (B) is likely to be decomposed by a hindered amine-based
light stabilizer. Accordingly, when the aromatic polycarbonate
resin (B) is large in the ratio of the polycarbonate resin (A) and
the aromatic polycarbonate resin (B), the amount of the light
stabilizer added is preferably set to be smaller.
[Release Agent]
As a release agent for imparting mold releasability at the time of
molding, the polycarbonate resin composition may contain from
0.0001 to 2 parts by weight of a fatty acid ester of a polyhydric
alcohol per 100 parts by weight of the polycarbonate resin. When
the amount of the fatty acid ester of a polyhydric alcohol is
adjusted to the range above, the effect of addition is sufficiently
obtained, and a molded article can be more reliably prevented from
cracking due to a release failure at the time of demolding in the
molding processing. Furthermore, in this case, clouding of the
resin composition or increase of deposits attached to the mold at
the time of molding processing can be more successfully suppressed.
The content of the fatty acid ester of a polyhydric alcohol is more
preferably from 0.01 to 1.5 parts by weight, and still more
preferably from 0.1 to 1 parts by weight.
The fatty acid ester of a polyhydric alcohol is preferably a
partial ester or whole ester of a polyhydric alcohol having a
carbon number of 1 to 20 with a saturated fatty acid having a
carbon number of 10 to 30. The partial ester or whole ester of a
polyhydric alcohol with a saturated fatty acid includes stearic
acid monoglyceride, stearic acid diglyceride, stearic acid
triglyceride, stearic acid monosorbitate, behenic acid
monoglyceride, pentaerythritol monostearate, pentaerythritol
distearate, pentaerythritol tetrastearate, pentaerythritol
tetrapelargonate, propylene glycol monostearate, isopropyl
palmitate, sorbitan monostearate, etc. Among these, stearic acid
monoglyceride, stearic acid triglyceride, and pentaerythritol
tetrastearate are preferably used.
In view of heat resistance and moisture resistance, a whole ester
is more preferred as the fatty acid ester of a polyhydric
alcohol.
The fatty acid is preferably a higher fatty acid, more preferably a
saturated fatty acid having a carbon number of 10 to 30. Such a
fatty acid includes myristic acid, lauric acid, palmitic acid,
stearic acid, behenic acid, etc.
In the fatty acid ester of a polyhydric alcohol, the polyhydric
alcohol is preferably ethylene glycol. In this case, when it is
added to the resin, the mold releasability can be enhanced without
impairing the transparency of the resin.
In addition, the fatty acid ester of a polyhydric alcohol is
preferably a fatty acid diester of a dihydric alcohol. In this
case, when it is added to the resin, reduction in the molecular
weight of the resin composition under a wet heat environment can be
suppressed.
In the present embodiment, the timing and method for adding the
release agent to be blended in the polycarbonate resin composition
are not particularly limited. The timing of addition includes, for
example, in the case of producing the polycarbonate resin by
transesterification method, the time when the polymerization
reaction is completed; irrespective of the polymerization method,
the time when the polycarbonate resin is in the melted state, such
as in the middle of kneading of the polycarbonate resin composition
and other compounding ingredients; and the time when blending and
kneading with the polycarbonate resin in a solid state, such as
pellet or powder, is performed using an extruder etc. As the
addition method, a method of mixing or kneading the release agent
directly with the polycarbonate resin composition may be employed;
or the release agent may be added as a high-concentration
masterbatch produced using the release agent and a small amount of
the polycarbonate resin composition or another resin, etc.
[Another Resin]
The polycarbonate resin composition may also be used as a polymer
alloy by kneading it with, for example, one member or two or more
members of a synthetic resin such as aromatic polyester, aliphatic
polyester, polyamide, polystyrene, polyolefin, acryl, amorphous
polyolefin, ABS and AS, and a biodegradable resin such as
polylactic acid and polybutylene succinate.
[Inorganic Filler, Organic Filler]
In the polycarbonate resin composition, as long as the design
property can be maintained, an inorganic filler such as glass
fiber, milled glass fiber, glass flake, glass bead, silica,
alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum
whisker, barium sulfate, talc, mica, calcium silicate (e.g.,
wollastonite), carbon black, graphite, iron powder, copper powder,
molybdenum disulfide, silicon carbide, silicon carbide fiber,
silicon nitride, silicon nitride fiber, brass fiber, stainless
steel fiber, potassium titanate fiber and a whisker thereof; a
powdery organic filler such as wood powder, bamboo powder, coconut
shell flour, cork flour and pulp powder; a balloon-like spherical
organic filler such as crosslinked polyester, polystyrene,
styrene-acrylic copolymer and urea resin; and a fibrous organic
filler such as carbon fiber, synthetic fiber and natural fiber, may
be added.
[Production Method of Polycarbonate Resin Composition]
The polycarbonate resin composition above can be produced by
performing an addition step of adding from 0.5 to 1,000 ppm by
weight, in terms of metal amount, of the specific compound (C) to
those specific polycarbonate resin (A) and aromatic polycarbonate
resin (B), and then performing a reaction step of melt-reacting the
polycarbonate resin (A) with the aromatic polycarbonate resin (B).
In the reaction step, by virtue of the presence of the compound
(C), the transesterification reaction of the polycarbonate resin
(A) with the aromatic polycarbonate resin (B) is promoted, and a
resin composition with high compatibility is obtained. Here, as the
polycarbonate resin (A), the aromatic polycarbonate resin (B) and
the compound (C), the same as those described above can be
used.
The polycarbonate resin composition can be produced by mixing the
above-described components in a predetermined ratio at the same
time or in an arbitrary order by means of a mixing machine such as
tumbler, V-blender, Nauta mixer, Banbury mixer, kneading roll or
extruder. Among others, a mixing machine enabling mixing in a
reduced-pressure state at the time of melt-mixing is more
preferred.
As to the melt-kneader, although whether the type is a twin-screw
extruder or a single-screw extruder is not limited as long as it
has a configuration capable of achieving mixing in the
reduced-pressure state, for the purpose of achieving reactive
mixing according to the properties of the specific polycarbonate
resin (A) and aromatic polycarbonate resin (B) used, a twin-screw
extruder is more preferred.
The mixing temperature of the polycarbonate resin composition is
preferably from 200 to 300.degree. C. In this case, the time
required for the reactive kneading can be shortened, and the amount
of the compound (C) necessary for the reaction can reduced. As a
result, not only degradation of the resin or deterioration of the
color tone can be more reliably prevented but also physical
properties on practical side, such as impact resistance and wet
heat resistance, can be more enhanced. From the same viewpoint, the
mixing temperature is more preferably from 220 to 280.degree.
C.
As to the mixing time, useless elongation thereof must be avoided
from the viewpoint of more reliably avoiding degradation of the
resin, similarly to the above, and although it is based on a
balance with the amount of the compound (C) or the mixing
temperature, the mixing time is preferably from 10 to 150 seconds,
and more preferably from 10 to 25 seconds. The conditions as to the
amount of the compound (C) and the mixing temperature must be set
to satisfy the range above.
The melt-reaction in the reaction step is preferably performed
under the condition of a vacuum degree of 30 kPa or less. The
degree of vacuum is more preferably 25 kPa or less, still more
preferably 15 kPa or less. The degree of vacuum as used herein
indicates an absolute pressure and is a value calculated according
to the conversion formula (101 kPa-(numerical value of vacuum
pressure gauge)) after reading a vacuum pressure gauge.
The reaction step is performed under reduced pressure, and the
condition of reduced pressure is controlled to the specific range
above, whereby in the reaction step, removal of a byproduct that
may be produced at the time of transesterification reaction of the
polycarbonate resin (A) and the aromatic polycarbonate resin (B) is
facilitated. This makes it easy for the transesterification
reaction to proceed, as a result, a resin composition with higher
compatibility between the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) can be produced.
[Molded Body]
The polycarbonate resin composition can be molded by a commonly
known method such as injection molding method, extrusion molding
method and compression molding method. The molded body obtained by
molding has excellent transparency and at the same time, possesses
high levels of biogenic substance content rate, heat resistance,
wet heat resistance and impact resistance in a balanced manner.
Furthermore, in the molded body obtained by molding the
polycarbonate resin composition, it is also possible to enhance the
color tone, weather resistance, mechanical strength, etc. or
decrease the amount of residual low-molecular components or foreign
matters. Accordingly, the molded body is suitable for vehicular
interior parts.
The above-described polycarbonate resin composition is excellent in
the color hue, transparency, heat resistance, weather resistance,
mechanical strength, etc. and furthermore, excellent in the color
hue under wet heat conditions or stability of optical properties
and therefore, can be applied to a wide range of fields including
the injection molding field such as electric/electronic parts,
automotive parts and glass substitute application; the extrusion
molding field such as film or sheet field and bottle or container
field; the lens application such as camera lens, finder lens and
CCD (Charged Coupled Device) or CMOS (Complementary Metal Oxide
Semiconductor) lens; an optical film or optical sheet used for a
liquid crystal or organic EL (Electro Luminescence) display, etc.,
such as retardation film, diffusion sheet, light guide plate and
polarizing film; an optical disc, an optical material, and an
optical part; and a binder application for fixing a coloring
matter, a charge transfer agent, etc.
The above-described polycarbonate resin composition is excellent in
the transparency, heat resistance, weather resistance, mechanical
strength, etc. and furthermore, excellent in the image clarity even
when colored with a coloring agent, etc. and therefore, can be
applied to an application such as automotive interior/exterior
parts, electric/electronic parts and housing. The automotive
exterior part includes, for example, fender, bumper, facia, door
panel, side garnish, pillar, radiator grill, side protector, side
molding, rear protector, rear molding, various spoilers, hood, roof
panel, trunk lid, detachable top, wind reflector, mirror housing,
and outer door handle. The automotive interior part includes, for
example, instrumental panel, center console panel, meter parts,
various switches, car navigation parts, car audio visual parts, and
automobile computer parts. The electric/electronic parts and
housing include, for example, an exterior part of personal
computers such as desktop and notebook, an exterior part of OA
(Office Automation) devices such as printer, copier, scanner and
facsimile (including a multifunction machine of these), an exterior
part of display devices (e.g., CRT, liquid crystal, plasma,
projector, organic EL), an exterior part of mouses, etc., switch
mechanism parts such key of keyboard and several switches, and an
exterior part of game machines (e.g., home game machine, arcade
game machine, pinball machine, slot machine). Furthermore, the
equipment includes electric OA equipment and household electric
appliances, such as personal digital assistance (so-called PDA),
cellular phone, portable book (e.g., dictionaries), portable
television set, drive for recording media (e.g., CD, MD, DVD,
next-generation high density disc, hard disc), reader for recording
media (e.g., IC card, smart media, memory stick), optical camera,
digital camera, parabolic antenna, electric tool, VTR, iron, hair
dryer, rice cooker, microwave oven, hot plate, audio equipment,
lighting equipment, refrigerator, air conditioner, air cleaner,
negative ion generator and clock.
EXAMPLES
Although the present invention is described in greater detail below
by referring to Examples, the present invention is not limited by
the following Examples as long as its gist is observed.
Test Example 1
Examples 1-1 to 1-24 and Comparative Examples 1-1 to 1-4
[Evaluation Method I]
In the following Production Examples, Examples 1-1 to 1-24 and
Comparative Examples 1-1 to 1-4, the physical properties or
characteristics of the polycarbonate resin (A), the aromatic
polycarbonate resin (B) and the resin composition were evaluated by
the following methods.
(I-1) Measurement of Reduced Viscosity
A sample of the polycarbonate resin (A) or the aromatic
polycarbonate resin (B) was dissolved in methylene chloride to
prepare a polycarbonate resin solution having a concentration of
0.6 g/dL. The transit time to of the solvent and the transit time t
of the solution were measured using an Ubbelohde viscometer
manufactured by Moritomo Rika Kogyo Co., Ltd. under the condition
of a temperature of 20.0.degree. C..+-.0.1.degree. C., and the
relative viscosity .eta..sub.rel was calculated according to the
following formula (i). Subsequently, from the relative viscosity
.eta..sub.rel, the specific viscosity .eta..sub.sp was determined
according to the following formula (ii): .eta..sub.rel=t/t.sub.0
(i) .eta..sub.sp=.eta..sub.rel-1 (ii)
The obtained specific viscosity .eta..sub.sp was divided by the
concentration c (g/dL) of the solution to thereby determine the
reduced viscosity (.eta..sub.sp/C). A higher value of the reduced
viscosity means a larger molecular weight.
(I-2) Measurement of Melt Viscosity
The melt viscosity of the polycarbonate resin composition was
measured using a capillary rheometer, "CAPILOGRAPH 1B",
manufactured by Toyo Seiki Seisaku-Sho, Ltd. under the conditions
of a die diameter of 1 mm, a die length of 10 mm, an inflow angle
of 90.degree. C., a preheating time of 2 minutes, a measurement
temperature of 240.degree. C., and a shear rate in the range of
12.16 to 6,080 sec.sup.-1 and is a value at a shear rate (SR) of
91.2 sec.sup.-1. In the measurement of the melt viscosity of the
polycarbonate resin, the polycarbonate resin used for the
measurement was previously dried at 90.degree. C. for 4 hours or
more. The ideal viscosity is a value obtained by multiplying the
melt viscosity of each component of the polycarbonate resin
composition by the blending ratio (% by weight) and summing the
resulting values, and the ratio to the ideal viscosity is a value
obtained by dividing the melt viscosity of the polycarbonate resin
composition by the ideal viscosity and multiplying the resulting
value by 100.
(I-3) Measurement of Glass Transition Temperature (Tg)
Tg of the polycarbonate resin composition is a value of Tmg
determined in conformity with the method of JIS-K7121 (1987) from a
DSC curve obtained when using a differential scanning calorimeter,
"DSC7", manufactured by Perkin Elmer, Inc. and subjecting the resin
composition, in a nitrogen gas atmosphere, to temperature rise to
200.degree. C. from 25.degree. C. at a heating rate of 20.degree.
C./min, holding at 200.degree. C. for 3 minutes, temperature drop
to 25.degree. C. at a cooling rate of 20.degree. C./min, holding at
25.degree. C. for 3 minutes, and again temperature rise to
200.degree. C. at a heating rate of 5.degree. C./min. Furthermore,
the singularity in the glass transition temperature was evaluated.
Specifically, the singularity was rated "A" when the DSC curve had
a single peak, and rated "C" when the DSC curve had a plurality of
peaks.
(I-4) Measurement of Metal Amount in Polycarbonate Resin
Composition
The metal amount in the polycarbonate resin composition was
measured using ICP-MS (inductively coupled plasma mass
spectrometer). Specifically, about 0.5 g of a sample of the
polycarbonate resin composition was accurately weighed and
subjected to closed pressure decomposition with sulfuric acid and
nitric acid. For the closed pressure decomposition, a microwave
decomposer, MULTIWAV, manufactured by PerkinElmer, Inc. was used.
The solution resulting from decomposition was appropriately diluted
with pure water and measured by ICP-MS (ELEMENT, manufactured by
ThermoQuest). The alkali and alkaline earth metals determined were
Li, Na, K, Cs, Mg, Ca, and Ba. Incidentally, the metal amount in
Examples 1-1 to 1-24 includes not only metals derived from the
compound (C) but also metals (e.g., Ca) derived from the
polycarbonate resin (A) or metals (e.g., Cs) derived from the
aromatic polycarbonate resin (B).
(I-5) Measurement of Total Light Transmittance
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain an injection-molded plate (100 mm (width).times.100 mm
(length).times.2 mm (thickness)). The total light transmittance of
the injection-molded plate was measured in conformity to JIS K7136
(2000) with a D65 light source by using a haze meter, "NDH2000",
manufactured by Nippon Denshoku Industries Co., Ltd. Here, a total
light transmittance of 80% or more was judged to have passed, and
when the injection-molded plate was apparently opaque by visual
observation, the evaluation result was shown as "opaque" instead of
the measured value of the total light transmittance.
(I-6) Wet Heat Resistance Test
A constant-temperature and constant-humidity bath, "HIFLEX FX224P",
manufactured by Kusumoto Chemicals, Ltd. was set to 80.degree. C.
and 95% RH or to 85.degree. C. and 85% RH, and a test piece of 100
mm or 50 mm (width).times.100 mm (length).times.2 mm (thickness)
was left standing still in the bath for 120 hours or 240 hours to
apply a wet heat treatment. Thereafter, the test piece was taken
out and measured for the haze, and a difference (.DELTA.Haze) from
the haze before the wet heat resistance test was determined.
Incidentally, the measurement of haze was performed in conformity
to JIS-K7136 (2000) by using a haze meter, "NDH2000", manufactured
by Nippon Denshoku Industries Co., Ltd. A larger value of
.DELTA.Haze means worse wet heat resistance, and a smaller value
means better wet heat resistance. Here, when the injection-molded
plate was opaque by visual observation in the measurement of the
total light transmittance, implementation of this test (wet heat
resistance test) was omitted.
(I-7) Heat Resistance Test
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain a multi-purpose test piece Type A described in JIS-K7139
(2009). A test piece having a length of 80 mm, a width of 10 mm and
a thickness of 4 mm was cut out from the obtained multi-purpose
test piece and measured for the deflection temperature under load
by Method A (bending stress applied to test piece: 1.80 MPa) in
conformity to JIS-K7191-2 (2007). In this test, a deflection
temperature under load of 90.degree. C. or more was judged to have
passed, and the deflection temperature under load is preferably
95.degree. C. or more, more preferably 100.degree. C. or more.
(I-8) High-Rate Test
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain an injection-molded plate (100 mm (width).times.100 mm
(length).times.2 mm (thickness)). A high-rate test of the obtained
injection-molded plate was conducted using "Shimadzu Hydroshot
Model HITS-P10" manufactured by Shimadzu Corp. under the conditions
of a temperature of 23.degree. C. or -20.degree. C., a striker
diameter of 5/8 inches, a support base diameter of 40 mm, and a
test speed of 4.4 m/s. The ductile fracture rate was determined by
dividing the scores of ductile-fractured samples out of samples
evaluated on a 5-score scale by evaluation scores and multiplying
the resulting value by 100.
(I-9) Measurement of Biogenic Substance Content Rate
Radiocarbon 14 (C.sup.14) is produced at a constant rate by a
cosmic ray in the atmosphere and lost at a constant rate
(half-life: 5,370 years) and therefore, is present in a constant
amount in nature. Although plants taking up carbon dioxide in the
atmosphere contains a constant amount of C.sup.14, when carbon
dioxide assimilation ceases due to milling, etc., the radiocarbon
is lost at a constant rate, and radioactive dating is established
by utilizing this property. Fossil fuel is not subject to the
effect of a cosmic ray for a long time and is therefore deprived of
all C.sup.14. On the other hand, in the case of a bio-derived
chemical, a long time has not passed since a stop of the supply of
C.sup.14, and it can be said that the C.sup.14 content is almost at
a constant value.
The method for calculating the biogenic substance content by using
the above-described method is specifically described. First, the
ISB carbonate constitutional unit of ISB-PC consists of 6 carbons
of bio-derived ISB and 1 DPC-derived carbon of fossil fuel and
therefore, the biogenic substance content rate of ISB-PC is number
of bio-derived carbons: 6/number of all carbons: 7=85.7%. Here, the
effect of a terminal is neglected, because the polymer chain is
sufficiently long. In the case of a copolymerized polycarbonate
resin as in Production Example 1-1 described later, since CHDM is a
fossil fuel-derived raw material, the biogenic substance content of
CHDM-PC is number of bio-derived carbons: 0/number of all carbons:
9=0%. In the case of ISB/CHDM=70/30 mol % of Production Example
1-1, only the ISB-PC component is bio-derived and therefore, the
biogenic substance content rate is 85.7%.times.70 mol %=60%.
Next, in the case of a blend of a polycarbonate resin (A) and an
aromatic polycarbonate resin (B) as in Examples, since the aromatic
polycarbonate resin (B) is a polymer produced from a fossil
fuel-derived raw material, the biogenic substance content rate is
0%. In Examples where the resins are blended on a weight ratio
basis, the molar mass (unit: g/mol) of each polycarbonate resin is
calculated, the weight of each is divided by the molar mass, and
the resulting value is converted to the molar fraction. Then, the
biogenic substance content of the blend is calculated from the
product of the biogenic substance content of the polycarbonate
resin (A) and the molar fraction thereof. Incidentally, with
respect to the calculation of the biogenic substance, the content
rate is calculated only with resin components, and the components
such as compound (C), heat stabilizer and release agent are not
taken into account.
[Raw Materials Used]
The abbreviations and manufacturers of the compounds used in
Examples and Comparative Examples below are as follows.
<Dihydroxy Compound>
ISB: Isosorbide [produced by Roquette Froeres] CHDM:
1,4-Cyclohexanedimethanol [produced by SK Chemicals] TCDDM:
Tricyclodecane dimethanol [produced by OXEA] BPC:
2,2-Bis(4-hydroxy-3-methylphenyl)propane [produced by Honshu
Chemical Industry Co., Ltd.] <Carbonic Acid Diester> DPC:
Diphenyl carbonate [produced by Mitsubishi Chemical Corporation]
<Catalyst Deactivator (Acidic Compound (E)> Phosphorous acid
[produced by Taihei Chemical Industrial Co., Ltd.] (molecular
weight: 82.0) <Heat Stabilizer (Antioxidant)> Irganox 1010:
Pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
[produced by BASF] AS2112: Tris(2,4-di-tert-butylphenyl)phosphite
[produced by ADEKA Corporation](molecular weight: 646.9)
<Release Agent> E-275: Ethylene glycol distearate [produced
by NOF Corporation] [Production Example 1-1 of Polycarbonate Resin
(A)]
Using continuous polymerization equipment consisting of three
vertical stirring reactors, one horizontal stirring reactor and a
twin-screw extruder, polymerization of a polycarbonate resin was
performed. Specifically, each of ISB, CHDM and DPC was dissolved in
a tank, and ISB, CHDM and DPC were continuously fed to the first
vertical stirring reactor at a flow rate of 35.2 kg/hr, 14.9 kg/hr
and 74.5 kg/hr, respectively (in a molar ratio of
ISB/CHDM/DPC=0.700/0.300/1.010). Simultaneously, an aqueous
solution of calcium acetate monohydrate was fed to the first
vertical stirring reactor such that the amount added of calcium
acetate monohydrate as a catalyst becomes 1.5 .mu.mol per mol of
all dihydroxy compounds. The reaction temperature, internal
pressure and residence time of each reactor were: first vertical
stirring reactor: 190.degree. C., 25 kPa and 90 minutes, second
vertical stirring reactor: 195.degree. C., 10 kPa and 45 minutes,
third vertical stirring reactor: 210.degree. C., 3 kPa and 45
minutes, fourth horizontal stirring reactor: 225.degree. C., 0.5
kPa and 90 minutes. The operation was performed while finely
controlling the internal pressure of the fourth horizontal reactor
such that the reduced viscosity of the obtained polycarbonate resin
becomes from 0.41 to 0.43 dL/g.
The polycarbonate resin was withdrawn at an amount of 60 kg/hr from
the fourth horizontal stirring reactor, and the resin in the molten
state was fed to a vented twin-screw extruder [TEX30.alpha.,
manufactured by The Japan Steel Works, Ltd., L/D: 42.0, L (mm):
length of screw, D (mm): diameter of screw]. The polycarbonate
resin having passed through the extruder was subsequently passed in
the molten state through a candle-type filter (made of SUS316)
having an opening size of 10 .mu.m to filter foreign matters.
Thereafter, the polycarbonate resin was discharged in the form of a
strand from a die, water-cooled, solidified and then pelletized by
a rotary cutter to obtain pellets of a copolymerized polycarbonate
resin having a molar ratio of ISB/CHDM of 70/30 mol %.
The extrude has three vacuum vent ports, and residual low molecular
components in the resin were devolatilized and removed there.
Before the second vent, 2,000 ppm by weight of water relative to
the resin was added to perform water-pouring devolatilization.
Before the third vent, Irganox 1010, AS2112, and E-275 were added
in an amount of 0.1 parts by weight, 0.05 parts by weight, and 0.3
parts by weight, respectively, per 100 parts by weight of the
polycarbonate resin. In this way, an ISB/CHDM copolymerized
polycarbonate resin was obtained. To the polycarbonate resin, 0.65
ppm by weight of phosphorous acid (0.24 ppm by weight as the amount
of phosphorus atom) was added as a catalyst deactivator. Here, the
phosphorous acid was added as follows. A masterbatch was prepared
by coating and mixing the pellets of the polycarbonate resin
obtained in Production Example 1-1 with an ethanol solution of
phosphorous acid, and fed before the first vent port of the extrude
(from the resin feed port side of the extruder) such that the
amount of the masterbatch becomes 1 part by weight per 100 parts by
weight of the polycarbonate resin in the extruder.
The polycarbonate resin (A) obtained in Production Example 1-1 is
designated as "PC-A1". The melt viscosity (240.degree. C., shear
rate: 91.2 sec.sup.-1) of PC-A1 was 720 Pas.
[Production Example 1-2 of Polycarbonate Resin (A)]
A polycarbonate resin having a molar ratio of ISB/CHDM of 50/50 mol
% was obtained by manufacturing the resin in the same manner as in
Production Example 1-1 except that the amounts of respective raw
materials fed to the reactor were changed to 25.4 kg/hr of ISB,
25.0 kg/hr of CHDM, and 74.8 kg/hr of DPC (as a molar ratio,
ISB/CHDM/DPC=0.500/0.500/1.006), the amount of calcium acetate
monohydrate per mol of all dihydroxy compounds was changed to 1.5
.mu.mol, and the reduced viscosity of the obtained polycarbonate
resin was adjusted to become from 0.60 to 0.63 dL/g. To the
polycarbonate resin, 0.65 ppm by weight of phosphorous acid (0.24
ppm by weight as the amount of phosphorus atom) was added as a
catalyst deactivator. Here, the phosphorous acid was added as
follows. A masterbatch was prepared by coating and mixing the
pellets of the polycarbonate resin obtained in Production Example
1-2 with an ethanol solution of phosphorous acid, and fed before
the first vent port of the extrude (from the resin feed port side
of the extruder) such that the amount of the masterbatch becomes 1
part by weight per 100 parts by weight of the polycarbonate resin
in the extruder.
The polycarbonate resin (A) obtained in Production Example 1-2 is
designated as "PC-A2". The melt viscosity (240.degree. C., shear
rate: 91.2 sec.sup.-1) of PC-A2 was 1,120 Pas.
[Production Example 1-3 of Polycarbonate Resin (A)]
Into a polymerization reaction apparatus equipped with a reflux
condenser controlled to a temperature of 100.degree. C. and a
stirring blade, ISB, CHDM and DPC purified by distillation to a
chloride ion concentration of 10 ppb or less were charged to have a
molar ratio of ISB/CHDM/DPC=0.27/0.73/1.00, and furthermore, an
aqueous solution of calcium acetate monohydrate was charged such
that the amount added of calcium acetate monohydrate as a catalyst
becomes 1.5 .mu.mol per mol of all dihydroxy compounds. After
thorough purging with nitrogen, the system was heated by a heating
medium and at the point when the internal temperature reached
100.degree. C., stirring was started to melt and homogenize the
contents under control to keep the internal temperature at
100.degree. C. Thereafter, temperature rise was started and by
adjusting the internal temperature to reach 210.degree. C. over 40
minutes, at the point when the internal temperature reached
210.degree. C., the system was controlled to keep this temperature.
At the same time, pressure reduction was started, and the internal
pressure was adjusted to reach 13.3 kPa (absolute pressure,
hereinafter the same) in 90 minutes after reaching the internal
temperature of 210.degree. C. While keeping the pressure above, the
system was held for another 30 minutes. Phenol vapor generated as a
byproduct along with the polymerization reaction was introduced
into the reflux condenser using, as a cooling medium, steam
controlled to 100.degree. C. in terms of the temperature at the
inlet to the reflux condenser, and monomer components contained in
a slight amount in the phenol vapor were returned to the
polymerization reactor. Uncondensed phenol vapor was subsequently
introduced into a condenser using, as a cooling medium, warm water
at 45.degree. C. and recovered. After the pressure was once
returned to atmospheric pressure, the thus-oligomerized contents
were transferred to another polymerization reaction apparatus
equipped with a stirring blade and a reflux condenser controlled in
the same manner as above and by starting temperature rise and
pressure reduction, the internal temperature and the pressure were
adjusted to reach 210.degree. C. and 200 Pa, respectively, over 60
minutes. Thereafter, the internal temperature and the pressure were
adjusted to reach 220.degree. C. and 133 Pa or less, respectively,
over 20 minutes, and at the point when a predetermined stirring
power was achieved, the pressure was recovered. A polycarbonate
resin in the molten state discharged from the outlet of the
polymerization reaction apparatus was pelletized by a pelletizer to
obtain pellets. The reduced viscosity was 0.63 dl/g.
In this way, a polycarbonate resin having a molar ratio of ISB/CHDM
of 27/73 mol % was obtained. The polycarbonate resin (A) obtained
in Production Example 1-3 is designated as "PC-A3". The melt
viscosity (240.degree. C., shear rate: 91.2 sec.sup.1-) of PC-A3
was 640 Pas.
[Production Example 1-4 of Polycarbonate Resin (A)]
Into a polymerization reaction apparatus equipped with a reflux
condenser controlled to a temperature of 100.degree. C. and a
stirring blade, ISB, TCDDM and DPC purified by distillation to a
chloride ion concentration of 10 ppb or less were charged to have a
molar ratio of ISB/TCDDM/DPC=0.70/0.30/1.00, and furthermore, an
aqueous solution of calcium acetate monohydrate was charged such
that the amount added of calcium acetate monohydrate as a catalyst
becomes 1.5 .mu.mol per mol of all dihydroxy compounds. By
performing thorough purging with nitrogen, the oxygen concentration
within the reaction apparatus was adjusted to be from 0.0005 to
0.001 vol %. Subsequently, the system was heated by a heating
medium and at the point when the internal temperature reached
100.degree. C., stirring was started to melt and homogenize the
contents under control to keep the internal temperature at
100.degree. C. Thereafter, temperature rise was started and by
adjusting the internal temperature to reach 210.degree. C. over 40
minutes, at the point when the internal temperature reached
210.degree. C., the system was controlled to keep this temperature.
At the same time, pressure reduction was started, and the pressure
was adjusted to reach 13.3 kPa in 90 minutes after reaching
210.degree. C. While keeping this pressure, the system was held for
another 60 minutes. Phenol vapor generated as a byproduct along
with the polymerization reaction was introduced into the reflux
condenser using, as a cooling medium, steam controlled to
100.degree. C. in terms of the temperature at the inlet to the
reflux condenser, and dihydroxy compound and carbonic acid diester
contained in a slight amount in the phenol vapor were returned to
the polymerization reactor. Uncondensed phenol vapor was
subsequently introduced into a condenser using, as a cooling
medium, warm water at 45.degree. C. and recovered. After the
pressure was once returned to atmospheric pressure, the
thus-oligomerized contents were transferred to another
polymerization reaction apparatus equipped with a stirring blade
and a reflux condenser controlled in the same manner as above and
by starting temperature rise and pressure reduction, the internal
temperature and the pressure were adjusted to reach 220.degree. C.
and 200 Pa, respectively, over 60 minutes. Thereafter, the internal
temperature and the pressure were adjusted to reach 230.degree. C.
and 133 Pa or less, respectively, over 20 minutes, and at the point
when a predetermined stirring power was achieved, the pressure was
returned to atmospheric pressure. The contents were withdrawn in
the form of a strand, and the polycarbonate copolymer was
pelletized by a rotary cutter. In this way, a polycarbonate resin
having a molar ratio of ISB/TCDDM of 70/30 mol % was obtained. To
the polycarbonate resin, 0.65 ppm by weight of phosphorous acid
(0.24 ppm by weight as the amount of phosphorus atom) was added.
Here, the phosphorous acid was added as follows. A masterbatch was
prepared by coating and mixing the pellets of the polycarbonate
resin obtained in Production Example 1-4 with an ethanol solution
of phosphorous acid, and fed before the first vent port of the
extrude (from the resin feed port side of the extruder) such that
the amount of the masterbatch becomes 1 part by weight per 100
parts by weight of the polycarbonate resin in the extruder.
The polycarbonate resin (A) obtained in Production Example 1-4 is
designated as "PC-A4". The melt viscosity (240.degree. C., shear
rate: 91.2 sec.sup.-1) of PC-A4 was 1,120 Pas.
[Aromatic Polycarbonate Resin (B)]
PC-B1: Novarex 7022J produced by Mitsubishi Engineering-Plastics
Corp. (an aromatic polycarbonate resin containing 100 mol % of
bisphenol A constitutional unit, reduced viscosity (240.degree. C.,
shear rate: 91.2 sec.sup.-1): 3,260 Pas) PC-B2: An aromatic
polycarbonate resin obtained by the following Production Example.
PC-B3: APEC 1897 (an aromatic polycarbonate resin composed of a
copolymer of bisphenol A and
1,1-bis(4-hydroxy-3,3,5-trimethylphenyl)cyclohexane, melt viscosity
(240.degree. C., shear rate: 91.2 sec.sup.-1): unmeasurable due to
too high viscosity) [Production Example of Aromatic Polycarbonate
Resin (PC-B2)
An aqueous cesium carbonate solution was added to a mixture of
181.8 kg of BPC and 57.7 kg of DPC. The amount added was adjusted
such that the amount of cesium carbonate becomes 2.0 .mu.mol per
mol of BPC as a dihydroxy compound. The mixture was then charged
into a first reactor having an internal volume of 400 L and being
equipped with a stirrer, a heating medium jacket, a vacuum pump and
a reflux condenser. Next, an operation of reducing the pressure
within the first reactor to 1.33 kPa (10 Torr) and recovering the
atmospheric pressure with nitrogen was repeated 10 times, and the
inside of the first reactor was thereby purged with nitrogen.
Thereafter, the internal temperature of the first reactor was
gradually raised by flowing a heating medium at a temperature of
230.degree. C. to the heating medium jacket, and the mixture was
thereby melted. The molten mixture was then transferred to a second
reactor. Here, the second reactor has an internal volume of 400 L
and is equipped with a stirrer, a heating medium jacket, a vacuum
pump and a reflux condenser. The molten mixture within the second
reactor was stirred by a stirrer adjusted to a rotational speed of
60 rpm and at the same time, the internal temperature of the second
reactor was kept at 220.degree. C. by controlling the temperature
within the heating medium jacket. While distilling off phenol
generated as a byproduct by an oligomerization reaction of BPC and
DPC occurring inside of the second reactor, the pressure within the
second reactor was reduced to, in terms of absolute pressure, 13.3
kPa (100 Torr) from 101.3 kPa (760 Torr). The inside of the second
reactor was then stirred at a rotational speed of 30 rpm, the
internal temperature was raised by means of the heating medium
jacket, and the pressure within the second rector was reduced to,
in terms of absolute pressure, 13.3 kPa from 101.3 kPa. Thereafter,
phenol was removed outside the system by distillation by continuing
temperature rise and reducing the internal temperature to, in terms
of absolute pressure, 399 Pa (3 Torr) from 13.3 kPa. Furthermore,
temperature rise was continued and after the absolute pressure
within the second reactor reached 70 Pa (about 0.5 Torr), a
polycondensation reaction was performed by keeping the pressure (70
Pa). At this time, the stirring rotation number was set to 10 rpm
according to the stirring power, and the final internal temperature
within the second reactor was set to 275.degree. C. The
polycondensation reaction was completed when the stirrer of the
second reactor reached a predetermined stirring power. The
polymerization reaction time in the second reactor was 310 minutes.
In this way, an aromatic polycarbonate resin (PC-B2) was obtained.
The melt viscosity (240.degree. C., shear rate: 91.2 sec.sup.-1) of
PC-B2 was 3,040 Pas.
Example 1-1
In this Example, PC-A1 was used as the polycarbonate resin (A),
PC-B1 was used as the aromatic polycarbonate resin (B), and
powdered sodium hydrogencarbonate (produced by Wako Pure Chemical
Industries, Ltd., special grade) was used as the compound (C). More
specifically, 70 parts by weight of the polycarbonate resin (A), 30
parts by weight of the polycarbonate resin (B), and 20 ppm by
weight, in terms of metal (Na equivalent), of the compound (C) were
blended and kneaded using a twin-screw kneader (TEX-30.alpha.,
manufactured by The Japan Steel Works, Ltd. (L/D=52.5, L (mm):
length of screw, D (mm): diameter of screw)) to perform a
melt-reaction of the polycarbonate resin (A) and the aromatic
polycarbonate resin (B). The ratio of the total length L.sub.t of
the kneading zone to the diameter D (mm) of the kneader screw is 6
(L.sub.t/D=6), and the kneading conditions are a flow rate: 20
kg/h, a rotational speed of screw: 200 rpm, and a cylinder
temperature: 230.degree. C. The extruder has two vacuum vent ports,
and the kneading was performed under the condition of a vent vacuum
degree of 11 kPa. The resin composition after the melt-reaction by
kneading was extruded in the form of a strand and, through a water
cooling step, cut into a pellet shape to obtain pellets of the
polycarbonate resin composition.
Subsequently, the pellets obtained were dried by a hot-air dryer at
temperature of 100.degree. C. for 5 hours, and injection molding of
the pellet was then performed using a 75-ton injection molding
machine (EC-75, manufactured by Toshiba Machine Co., Ltd.). The
molding conditions are a mold temperature: 60.degree. C. and a
cylinder temperature: 240.degree. C. In this way, a test piece
composed of a plate-like molded body of 100 mm (width).times.100 mm
(length).times.2 mm (thickness)) was obtained. In addition, an ISO
tensile test piece was obtained by performing the molding in the
same manner. Using these test pieces, the above-described
evaluations were performed, and the results obtained are shown in
Table 1.
Example 1-2
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) and (2) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) The amount added (Na equivalent) of sodium hydrogencarbonate
used as the compound (C) was changed to 10 ppm from 20 ppm.
(2) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-3
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) The amount added (Na equivalent) of sodium hydrogencarbonate
used as the compound (C) was changed to 10 ppm from 20 ppm.
(2) At the time of again performing melt kneading after
manufacturing a polycarbonate resin composition in the same manner
as in Example 1-1, an acidic compound (E) composed of phosphorous
acid was added as a catalyst deactivator. The amount added was 0.5
times by mol relative to the amount added of the compound (C).
(3) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-4
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) The amount added (Na equivalent) of sodium hydrogencarbonate
used as the compound (C) was changed to 10 ppm from 20 ppm.
(2) At the time of again performing melt kneading after
manufacturing a polycarbonate resin composition in the same manner
as in Example 1-1, an acidic compound (E) composed of phosphorous
acid was added as a catalyst deactivator. The amount added was 1
times by mol relative to the amount added of the compound (C).
(3) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-5
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) The amount added (Na equivalent) of sodium hydrogencarbonate
used as the compound (C) was changed to 10 ppm from 20 ppm.
(2) At the time of again performing melt kneading after
manufacturing a polycarbonate resin composition in the same manner
as in Example 1-1, an acidic compound (E) composed of phosphorous
acid was added as a catalyst deactivator. The amount added was 1.5
times by mol relative to the amount added of the compound (C).
(3) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-6
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) The amount added (Na equivalent) of sodium hydrogencarbonate
used as the compound (C) was changed to 10 ppm from 20 ppm.
(2) At the time of again performing melt kneading after
manufacturing a polycarbonate resin composition in the same manner
as in Example 1-1, an acidic compound (E) composed of phosphorous
acid was added as a catalyst deactivator. The amount added was 2
times by mol relative to the amount added of the compound (C).
(3) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-7
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (5) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to an aqueous sodium hydroxide solution having a concentration of
0.4% by weight. The amount added (Na equivalent) was 100 ppm.
(2) The total length of the kneading zone of the kneader screw was
changed to L/D=21.5 from L/D=6.
(3) The number of vacuum vent ports was changed to 1 from 2.
(4) The vent vacuum degree was changed to 21 kPa from 11 kPa.
(5) The flow rate in the kneading conditions was changed to 10 kg/h
from 20 kg/h.
Example 1-8
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) and (2) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to cesium carbonate (powder). The amount added (Cs equivalent) was
10 ppm by weight.
(2) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-9
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) and (2) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to cesium carbonate (powder). The amount added (Cs equivalent) was
5 ppm by weight.
(2) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-10
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to cesium carbonate (powder). The amount added (Cs equivalent) was
5 ppm by weight.
(2) At the time of again performing melt kneading after
manufacturing a polycarbonate resin composition in the same manner
as in Example 1-1, an acidic compound (E) composed of phosphorous
acid was added as a catalyst deactivator. The amount added was 2
times by mol relative to the amount added of the compound (C).
(3) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-11
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to sodium chloride (powder). The amount added (Na equivalent) was
100 ppm by weight.
(2) The total length of the kneading zone of the kneader screw was
changed to L/D=18 from L/D=6.
(3) The vent vacuum degree was changed to 21 kPa from 11 kPa.
Example 1-12
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) and (2) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
1.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 3 ppm by weight.
(2) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-13
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (3) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 3 ppm by weight.
(2) At the time of again performing melt kneading after
manufacturing a polycarbonate resin composition in the same manner
as in Example 1-1, an acidic compound (E) composed of phosphorous
acid was added as a catalyst deactivator. The amount added was 2
times by mol relative to the amount added of the compound (C).
(3) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-14
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) The blending ratio of the polycarbonate resin (A) was changed
to 90 parts by weight, and the blending ratio of the aromatic
polycarbonate resin (B) was changed to 10 parts by weight.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 3 ppm by weight.
(3) The flow rate in the kneading conditions was changed to 10 kg/h
from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-15
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) The blending ratio of the polycarbonate resin (A) was changed
to 50 parts by weight, and the blending ratio of the aromatic
polycarbonate resin (B) was changed to 50 parts by weight.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 3 ppm by weight.
(3) The flow rate in the kneading conditions was changed to 10 kg/h
from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-16
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) PC-A1 used as the polycarbonate resin (A) was changed to
PC-A4.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 3 ppm by weight.
(3) The flow rate in the kneading conditions was changed to 10 kg/h
from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-17
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) PC-B1 used as the aromatic polycarbonate resin (B) was changed
to PC-B2. The amount added was 5 ppm by weight.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 5 ppm by weight.
(3) The flow rate was changed to 10 kg/h from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-18
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) PC-B1 used as the aromatic polycarbonate resin (B) was changed
to PC-B3.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 5 ppm by weight.
(3) The flow rate was changed to 10 kg/h from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-19
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) PC-A1 used as the polycarbonate resin (A) was changed to
PC-A2.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to potassium carbonate (powder). The amount added (K equivalent)
was 3 ppm by weight.
(3) The flow rate was changed to 10 kg/h from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-20
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) PC-A1 used as the polycarbonate resin (A) was changed to
PC-A2.
(2) Sodium hydrogencarbonate used as the compound (C) was changed
to calcium hydroxide (powder). The amount added (Ca equivalent) was
500 ppm by weight.
(3) The flow rate was changed to 10 kg/h from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Example 1-21
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for a change in (1) below, and a
molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to sodium chloride (powder). The amount added (Na equivalent) was
10 ppm by weight.
Example 1-22
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for a change in (1) below, and a
molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to lithium acetate. The amount added (Li equivalent) was 10 ppm by
weight.
Example 1-23
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for a change in (1) below, and a
molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to lithium stearate. The amount added (Li equivalent) was 3 ppm by
weight.
Example 1-24
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for a change in (1) below, and a
molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
2.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to sodium orthosilicate. The amount added (Na equivalent) was 10
ppm by weight.
Comparative Example 1-1
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) and (2) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
3.
Incidentally, the polycarbonate resin composition of this Example
had a cesium amount of 0.2 ppm by weight and a calcium amount of
0.2 ppm by weight. The metal amounts were measured by the
above-described ICP-MS. In this Example, the compound (C) was not
added separately from the polycarbonate resin (A) and the aromatic
polycarbonate resin (B) at the time of production of the resin
composition and therefore, those metal amounts were derived from
the polycarbonate resin (A) and the aromatic polycarbonate resin
(B). The content of at least one kind of compound (C) selected from
compounds of Group 1 and Group II metals of the long-form periodic
table, contained in the polycarbonate resin composition of this
Example, was 0.4 ppm by weight. As to the metal amounts derived
from the polycarbonate resin (A) and the aromatic polycarbonate
resin (B), the same holds true for Comparative Examples 1-2 to 1-4
described later.
(1) The amount added of the compound (C) added at the time of
production of the resin composition was changed to 0.
(2) The vent vacuum degree was changed to 21 kPa from 11 kPa.
Comparative Example 1-2
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) to (4) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
3.
(1) PC-A1 used as the polycarbonate resin (A) was changed to
PC-A3.
(2) The amount added of the compound (C) was changed to 0.
(3) The flow rate was changed to 10 kg/h from 20 kg/h.
(4) The vent vacuum degree was changed to 6 kPa from 11 kPa.
Comparative Example 1-3
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for a change in (1) below, and a
molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
3.
(1) Sodium hydrogencarbonate used as the compound (C) was changed
to tetra-n-butoxytitanium (hereinafter, simply referred to as TBT).
The amount added was 1,000 ppm by weight.
Comparative Example 1-4
A polycarbonate resin composition was manufactured in the same
manner as in Example 1-1 except for changes in (1) and (2) below,
and a molded body (test piece) was manufactured using the resin
composition. Evaluation results of this Example are shown in Table
3.
(1) The vent vacuum degree was changed to 101 kPa from 11 kPa.
(2) The amount (Na equivalent) of sodium hydrogencarbonate used as
the compound (C) was changed to 10 ppm by weight.
TABLE-US-00001 TABLE 1 Example No. Example Example Example Example
Example Example Example Example Example E- xample Example Example
1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 1-12 Blending
Polycarbonate PC-A1 70 70 70 70 70 70 70 70 70 70 70 70 resin (A)
(parts PC-A2 -- -- -- -- -- -- -- -- -- -- -- -- by weight) PC-A3
-- -- -- -- -- -- -- -- -- -- -- -- PC-A4 -- -- -- -- -- -- -- --
-- -- -- -- Aromatic PC-B1 30 30 30 30 30 30 30 30 30 30 30 30
polycarbonate PC-B2 -- -- -- -- -- -- -- -- -- -- -- -- resin (B)
(parts PC-B3 -- -- -- -- -- -- -- -- -- -- -- -- by weight)
Compound (C) kind sodium sodium sodium sodium sodium sodium sodium
cesium- cesium cesium sodium potassium hydrogen hydrogen hydrogen
hydrogen hydrogen hydrogen hydroxide carbona- te carbonate
carbonate chloride carbonate carbonate carbonate carbonate
carbonate carbonate carbonate (aqueous (p- owder) (powder) (powder)
(powder) (powder) (powder) (powder) (powder) (powder) (powder)
(powder) solution) amount 20 10 10 10 10 10 100 10 5 5 100 3 added
(ppm by weight) Acidic kind -- -- phosphorous phosphorous
phosphorous phosphorous -- -- -- - phosphorous -- -- compound (E)
acid acid acid acid acid amount -- -- 0.5 1 1.5 2 -- -- -- 2 -- --
added (mol) Metal amount ppm by 20.5 10.5 10.5 10.5 10.5 10.5 100.7
10.5 5.5 5.5 100.4 3.5 (total) weight Properties Melt viscosity Pa
s 920 1390 1520 1500 1470 1500 160 1000 1680 1600 680 1470
@240.degree. C., SR = 91.2 s.sup.-1 Ratio of % 62 94 103 101 99 101
11 67 113 108 46 99 viscosity to ideal viscosity (/2020 Pa s) Glass
transition singularity A A A A A A A A A A A A temperature .degree.
C. 125 125 125 125 125 125 125 125 125 125 125 125 (DSC method)
Total light % 89.5 89.8 90.1 90.0 89.9 89.9 80.4 85.7 88.8 89.0
81.1 89 transmittance Haze % 0.7 0.5 0.4 0.6 0.4 0.3 1.8 0.3 0.6
0.3 1.5 0.2 Wet heat .DELTA.Haze 67.3 51.6 23.5 8.4 6.1 6.1 97.4 --
-- -- 31 -- resistance (80.degree. C. 95% RH_120 hr) Wet heat
.DELTA.Haze -- -- -- -- -- -- -- 0.1 0.2 0.2 -- 3.5 resistance
(85.degree. C. 85% RH_240 hr) Heat resistance .degree. C. 105 107
107 106 106 105 104 108 107 107 105 106 (DTUL_1.80 MPa) High-rate
test % 80 100 100 100 100 100 0 100 100 100 100 100 (23.degree.
C.), ductile fracture rate High-rate test (-20.degree. C.), % 20 20
80 20 40 60 0 40 0 100 0 80 ductile fracture rate Biogenic % 46.5
46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 substance
content rate (C.sup.14 estimation)
TABLE-US-00002 TABLE 2 Example No. Example Example Example Example
Example Example Example Example Example- Example 1-13 1-14 Example
1-15 1-16 1-17 1-18 1-19 1-20 1-21 Example 1-22 1-23 1-24 Blending
Polycarbonate PC-A1 70 90 50 -- 70 70 -- -- 70 70 70 70 resin (A)
PC-A2 -- -- -- -- -- -- 70 70 -- -- -- -- (parts by PC-A3 -- -- --
-- -- -- -- -- -- -- -- weight) PC-A4 -- -- -- 70 -- -- -- -- -- --
-- -- Aromatic PC-B1 30 10 50 30 -- -- 30 30 30 30 30 30
polycarbonate PC-B2 -- -- -- -- 30 -- -- -- -- -- -- -- resin (B)
(parts PC-B3 -- -- -- -- -- 30 -- -- -- -- -- -- by weight)
Compound (C) kind potassium potassium potassium potassium potassium
potas- sium potassium calcium sodium lithium lithium sodium
carbonate carbonate carbonate carbonate carbonate carbonate
carbonate h- ydroxide chloride acetate stearate ortho- (powder)
(powder) (powder) (powder) (powder) (powder) (powder) (powder)-
(powder) silicate amount 3 3 3 3 5 5 3 500 10 10 3 10 added (ppm by
weight) Acidic kind phosphorous -- -- -- -- -- -- -- -- -- -- --
compound (E) acid amount 2 -- -- -- -- -- -- -- -- -- -- -- added
(mol) Metal amount ppm by 3.5 3.3 3.4 3.4 5.8 5.3 3.5 500.5 10.4
10.4 10.4 10.4 (total) weight Properties Melt viscosity Pa s 1540
850 1300 1200 300 1220 780 1060 1100 820 860 680 @240.degree. C.,
SR = 91.2 s.sup.-1 Ratio of % 104 87 65 68 21 -- 43 59 74 55 58 46
viscosity to ideal viscosity (/2020 Pa s) Glass transition
singularity A A A A A A A A A A A A temperature .degree. C. 125 121
130 130 120 133 111 111 125 125 125 125 (DSC method) Total light %
89.1 88 86.5 86.9 82.2 82.8 83.9 89.7 88.0 88.0 90.0 87.0
transmittance Haze % 0.3 0.5 1.8 0.6 0.8 1 1.8 8 0.3 0.3 0.2 1.0
Wet heat .DELTA.Haze -- -- -- -- -- -- -- -- -- -- -- -- resistance
(80.degree. C. 95% RH_120 hr) Wet heat .DELTA.Haze 1.6 0 0 3.8 3.3
1.9 0.2 5.3 1.13 1.13 1.1 2.1 resistance (85.degree. C. 85% RH_240
hr) Heat resistance .degree. C. 106 100 110 111 98 110 92 92 107
107 107 107 (DTUL_1.80 MPa) High-rate test % 100 100 100 100 80 60
100 100 100 100 100 100 (23.degree. C.), ductile fracture rate
High-rate test (-20.degree. C.), % 60 20 80 0 0 0 100 40 0 0 0 0
ductile fracture rate Biogenic % 46.5 56 35.8 45.6 47.6 -- 33.3
33.3 46.5 46.5 46.5 46.5 substance content rate (C.sup.14
estimation)
TABLE-US-00003 TABLE 3 Comparative Example No. Comparative
Comparative Comparative Comparative Example 1-1 Example 1-2 Example
1-3 Example 1-4 Blending Polycarbonate resin (A) (parts by weight)
PC-A1 70 -- 70 70 PC-A2 -- -- -- -- PC-A3 -- 70 -- -- PC-A4 -- --
-- -- Aromatic polycarbonate resin (B) PC-B1 30 30 30 30 (parts by
weight) PC-B2 -- -- -- -- PC-B3 -- -- -- -- Compound (C) kind -- --
TBT sodium hydrogen- (liquid) carbonate (powder) amount added (ppm
by -- -- 1000 10 weight) Acidic compound (E) kind -- -- -- --
amount added (mol) -- -- -- -- Metal amount (total) ppm by weight
0.4 0.4 0.4 10.4 Properties Melt viscosity @240.degree. C. SR =
91.2 s.sup.-1 Pa s 1070 820 1100 1200 Ratio of viscosity to ideal
viscosity (/2020 Pa s) % 72 58 74 81 Glass transition temperature
(DSC method) singularity C A C C .degree. C. 122, 137 89 121, 136
122, 136 Total light transmittance % opaque 89.74 opaque opaque
Haze % -- 1.9 -- -- Wet heat resistance (80.degree. C. 95% RH_120
hr) .DELTA.Haze -- -- -- -- Wet heat resistance (85.degree. C. 85%
RH_240 hr) .DELTA.Haze -- 1.3 -- -- Heat resistance (DTUL_1.80 MPa)
.degree. C. 107 75 108 108 High-rate test (23.degree. C.), ductile
fracture rate % 0 100 0 0 High-rate test (-20.degree. C.), ductile
fracture rate % 0 100 0 0 Biogenic substance content rate (C.sup.14
estimation) % 46.5 18 46.5 46.5
As seen from Tables 1 to 3, the polycarbonate resin composition of
Examples contains a polycarbonate resin (A) containing a
constitutional unit derived from a compound represented by formula
(1), an aromatic polycarbonate resin (B), and at least one compound
(C) selected from the group consisting of compounds of Group I
metals of the long-form periodic table and compounds of Group II
metals of the long-form periodic table, in which the content of the
compound (C) is from 0.5 to 1,000 ppm by weight in terms of metal
amount in the compound (C). In such a polycarbonate resin
composition, the total light transmittance as a molded body having
a thickness of 2 mm was 80% or more, and the glass transition
temperature measured by differential scanning calorimetric analysis
was single. This polycarbonate resin composition had excellent
transparency and at the same time, possessed high levels of
biogenic substance content rate, heat resistance, wet heat
resistance and impact resistance in a balanced manner.
Test Examples 2
Examples 2-1 to 2-7, Comparative Examples 2-1 to 2-4, and Reference
Examples 2-1 and 2-2
Next, Examples, etc. of a polycarbonate resin composition
containing a polycarbonate resin (A), a aromatic polycarbonate
resin (B), a compound (C) and a crown ether compound (D) are
described.
[Evaluation Method II]
In the following, the physical properties or characteristics of the
polycarbonate resin (A), the aromatic polycarbonate resin (B) and
the resin composition were evaluated by the following methods.
(II-1) Measurement of Reduced Viscosity
A sample of the polycarbonate resin (A) or the aromatic
polycarbonate resin (B) was dissolved in methylene chloride to
prepare a polycarbonate resin solution having a concentration of
0.6 g/dL. The transit time to of the solvent and the transit time t
of the solution were measured using an Ubbelohde viscometer
manufactured by Moritomo Rika Kogyo Co., Ltd. under the condition
of a temperature of 20.0.degree. C..+-.0.1.degree. C., and the
relative viscosity .eta..sub.rel was calculated according to the
following formula (i). Subsequently, from the relative viscosity
.eta..sub.rel, the specific viscosity .eta..sub.sp was determined
according to the following formula (ii): .eta..sub.rel=t/t.sub.0
(i) .eta..sub.sp=.eta..sub.rel-1 (ii)
The obtained specific viscosity .eta..sub.sp was divided by the
concentration c (g/dL) of the solution to thereby determine the
reduced viscosity (.eta..sub.sp/c). A higher value of the reduced
viscosity means a larger molecular weight.
(II-2) Measurement of Glass Transition Temperature (Tg)
Tg of the polycarbonate resin composition is a value of Tmg
determined in conformity with the method of JIS-K7121 (1987) from a
DSC curve obtained when using a differential scanning calorimeter,
"DSC7", manufactured by Perkin Elmer, Inc. and subjecting the resin
composition, in a nitrogen gas atmosphere, to temperature rise to
200.degree. C. from 25.degree. C. at a heating rate of 20.degree.
C./min, holding at 200.degree. C. for 3 minutes, temperature drop
to 25.degree. C. at a cooling rate of 20.degree. C./min, holding at
25.degree. C. for 3 minutes, and again temperature rise to
200.degree. C. at a heating rate of 5.degree. C./min. Furthermore,
the singularity in the glass transition temperature was evaluated.
Specifically, the singularity was rated "A" when the DSC curve had
a single peak, and the singularity was rated "C" when the DSC curve
had a plurality of peaks.
(II-3) Measurement of Metal Amount in Polycarbonate Resin
Composition
The metal amount in the polycarbonate resin composition was
measured using ICP-MS (inductively coupled plasma mass
spectrometer). Specifically, about 0.5 g of a sample of the
polycarbonate resin composition was accurately weighed and
subjected to closed pressure decomposition with sulfuric acid and
nitric acid. For the closed pressure decomposition, a microwave
decomposer, MULTIWAV, manufactured by PerkinElmer, Inc. was used.
The solution resulting from decomposition was appropriately diluted
with pure water and measured by ICP-MS (ELEMENT, manufactured by
ThermoQuest). The alkali and alkaline earth metals determined were
Li, Na, K, Cs, Mg, Ca, and Ba. Incidentally, the metal amount in
Examples 2-1 to 2-7, Comparative Examples 2-1 to 2-4, and Reference
Examples 2-1 and 2-2 includes not only metals derived from the
compound (C) but also metals (e.g., Ca) derived from the
polycarbonate resin (A) or metals (e.g., Cs) derived from the
aromatic polycarbonate resin (B).
(II-4) Measurement of Total Light Transmittance
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain an injection-molded plate (100 mm (width).times.100 mm
(length).times.2 mm (thickness)). The total light transmittance of
the injection-molded plate was measured in conformity to JIS K7136
(2000) with a D65 light source by using a haze meter, "NDH2000",
manufactured by Nippon Denshoku Industries Co., Ltd. Here, a total
light transmittance of 80% or more was judged to have passed, and
when the injection-molded plate was apparently opaque by visual
observation, the evaluation result was shown as "opaque" instead of
the measured value of the total light transmittance.
(II-5) Wet Heat Resistance Test
A constant-temperature and constant-humidity bath, "HIFLEX FX224P",
manufactured by Kusumoto Chemicals, Ltd. was set to 85.degree. C.
and 85% RH, and a test piece of 100 mm or 50 mm (width).times.100
mm (length).times.2 mm (thickness) was left standing still in the
bath for 480 hours to apply a wet heat treatment. Thereafter, the
test piece was taken out and measured for the haze, and a
difference (.DELTA.Haze) from the haze before the wet heat
resistance test was determined. Incidentally, the measurement of
haze was performed in conformity to JIS-K7136 (2000) by using a
haze meter, "NDH2000", manufactured by Nippon Denshoku Industries
Co., Ltd. A larger value of .DELTA.Haze means worse wet heat
resistance, and a smaller value means better wet heat resistance.
Here, when the injection-molded plate was opaque by visual
observation in the measurement of the total light transmittance,
implementation of this test (wet heat resistance test) was
omitted.
(II-6) Heat Resistance Test
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain a multi-purpose test piece Type A described in JIS-K7139
(2009). A test piece having a length of 80 mm, a width of 10 mm and
a thickness of 4 mm was cut out from the obtained multi-purpose
test piece and measured for the deflection temperature under load
by Method A (bending stress applied to test piece: 1.80 MPa) in
conformity to JIS-K7191-2 (2007). In this test, although a
deflection temperature under load of 90.degree. C. or more was
judged to have passed, the deflection temperature under load is
preferably 95.degree. C. or more, more preferably 100.degree. C. or
more.
(II-7) High-Rate Test
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain an injection-molded plate (100 mm (width).times.100 mm
(length).times.2 mm (thickness)). A high-rate test of the obtained
injection-molded plate was conducted using "Shimadzu Hydroshot
Model HITS-P10" manufactured by Shimadzu Corp. under the conditions
of a temperature of 23.degree. C. or -20.degree. C., a striker
diameter of 5/8 inches, a support base diameter of 40 mm, and a
test speed of 4.4 m/s. The ductile fracture rate was determined by
dividing the scores of ductile-fractured samples out of samples
evaluated on a 5-score scale by evaluation scores and multiplying
the resulting value by 100.
(II-8) Bending Modulus
Pellets of the polycarbonate resin composition were dried at
90.degree. C. for 4 hours or more by using a hot-air dryer. The
dried pellets were then fed to an injection molding machine (Model
J75EII, manufactured by The Japan Steel Works, Ltd.) and molded
under the conditions of a resin temperature of 240.degree. C., a
mold temperature of 60.degree. C. and a molding cycle of 50 seconds
to obtain a multi-purpose test piece Type A described in JIS-K7139
(2009). A test piece having a length of 80 mm, a width of 10 mm and
a thickness of 4 mm was cut out from the obtained multi-purpose
test piece and measured for the bending modulus in conformity to
JIS-K7171 (2008).
(II-9) Measurement of Biogenic Substance Content Rate
Radiocarbon 14 (C.sup.14) is produced at a constant rate by a
cosmic ray in the atmosphere and lost at a constant rate
(half-life: 5,370 years) and therefore, is present in a constant
amount in nature. Although plants taking up carbon dioxide in the
atmosphere contains a constant amount of C.sup.14, when carbon
dioxide assimilation ceases due to milling, etc., the radiocarbon
is lost at a constant rate, and radioactive dating is established
by utilizing this property. Fossil fuel is not subject to the
effect of a cosmic ray for a long time and is therefore deprived of
all C.sup.14. On the other hand, in the case of a bio-derived
chemical, a long time has not passed since a stop of the supply of
C.sup.14, and it can be said that the C.sup.14 content has almost a
constant value.
The method for calculating the biogenic substance content by using
the above-described method is specifically described. First, the
ISB carbonate constitutional unit of ISB-PC consists of 6 carbons
of bio-derived ISB and 1 DPC-derived carbon of fossil fuel and
therefore, the biogenic substance content rate of ISB-PC is number
of bio-derived carbons: 6/number of all carbons: 7=85.7%. Here, the
effect of a terminal is neglected, because the polymer chain is
sufficiently long. In the case of a copolymerized polycarbonate
resin as in Production Example 1 described above, since CHDM is a
fossil fuel-derived raw material, the biogenic substance content of
CHDM-PC is number of bio-derived carbons: 0/number of all carbons:
9=0%. In the case of ISB/CHDM=70/30 mol % of Production Example
1-1, only the ISB-PC component is bio-derived and therefore, the
biogenic substance content rate is 85.7%.times.70 mol %=60%.
Next, in the case of a blend of a polycarbonate resin (A) and an
aromatic polycarbonate resin (B) as in Examples, since the aromatic
polycarbonate resin (B) is a polymer produced from a fossil
fuel-derived raw material, the biogenic substance content rate is
0%. In Examples where the resins are blended on a weight ratio
basis, the molar mass (unit: g/mol) of each polycarbonate resin is
calculated, the weight of each is divided by the molar mass, and
the resulting value is converted to the molar fraction. Then, the
biogenic substance content of the blend is calculated from the
product of the biogenic substance content of the polycarbonate
resin (A) and the molar fraction thereof. Incidentally, as to the
calculation of the biogenic substance, the content is calculated
only with resin components, and the components such as compound
(D), heat stabilizer and release agent are not taken into
account.
[Raw Materials Used]
The abbreviations and manufacturers of the compounds used in
Examples and Comparative Examples below are as follows.
<Dihydroxy Compound>
ISB: Isosorbide [produced by Roquette Froeres] CHDM:
1,4-Cyclohexanedimethanol [produced by SK Chemicals] <Carbonic
Acid Diester> DPC: Diphenyl carbonate [produced by Mitsubishi
Chemical Corporation] <Catalyst Deactivator (Acidic Compound
(E)> Phosphorous acid [produced by Taihei Chemical Industrial
Co., Ltd.] (molecular weight: 82.0) <Heat Stabilizer
(Antioxidant)> Irganox 1010:
Pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propi-
onate] [produced by BASF] AS2112:
Tris(2,4-di-tert-butylphenyl)phosphite [produced by ADEKA
Corporation](molecular weight: 646.9) <Release Agent> E-275:
Ethylene glycol distearate [produced by NOF Corporation]
[Polycarbonate Resin (A)]
As the polycarbonate resin (A), PC-A1 manufactured in Production
Example 1-1 or PC-A3 manufactured in Production Example 1-3 was
used. Specifically, this is shown in Tables 4 and 5 later.
[Polycarbonate Resin (B)]
As the aromatic polycarbonate resin (B), PC-B1 was used.
Specifically, this is shown in Tables 4 and 5 later.
[Compound (C)]
Sodium carbonate (produced by Wako Pure Chemical Industries, Ltd.,
special grade) Sodium hydrogencarbonate (produced by Wako Pure
Chemical Industries, Ltd., special grade) Cesium carbonate
(produced by Nacalai Tesque, Inc., special grade) [Crown Ether
Compound (D)] 18C6E (18-Crown-6-ether):
1,4,7,10,13,16-hexaoxacyclooctadecane (produced by Tokyo Chemical
Industry Co., Ltd.) 15C5E (15-Crown-5-ether):
1,4,7,10,13-pentaoxacyclopentadecane (produced by Tokyo Chemical
Industry Co., Ltd.) [Acidic Compound (E)] Phosphorous acid
(produced by Wako Pure Chemical Industries, Ltd., special
grade)
Example 2-1
In this Example, PC-A1 was used as the polycarbonate resin (A),
PC-B1 was used as the aromatic polycarbonate resin (B),
18-crown-6-ether was used as the crown ether compound (D), and
potassium carbonate was used as the compound (C). More
specifically, 70 parts by weight of the polycarbonate resin (A), 30
parts by weight of the aromatic polycarbonate resin (B), 1 times by
mol of the crown ether compound (D) relative to the compound (C),
and 2 ppm by weight, in terms of metal (K equivalent), of the
compound (C) were blended and kneaded using a twin-screw kneader
(TEX-30.alpha., manufactured by The Japan Steel Works, Ltd.
(L/D=52.5, L (mm): length of screw, D (mm): diameter of screw)) to
perform a melt-reaction of the polycarbonate resin (A) and the
aromatic polycarbonate resin (B). The ratio of the total length
L.sub.t of the kneading zone to the diameter D (mm) of the kneader
screw is 6 (L.sub.t/D=6), and the kneading conditions are a flow
rate: 10 kg/h, a rotational speed of screw: 200 rpm, and a cylinder
temperature: 230.degree. C. The extruder has two vacuum vent ports,
and the kneading was performed under the condition of a vent vacuum
degree of 11 kPa. The resin composition after the melt-reaction by
kneading was extruded in the form of a strand and, through a water
cooling step, cut into a pellet shape to obtain pellets of the
polycarbonate resin composition.
Subsequently, the pellets obtained were dried by a hot-air dryer at
temperature of 100.degree. C. for 5 hours, and injection molding of
the pellet was then performed using a 75-ton injection molding
machine (EC-75, manufactured by Toshiba Machine Co., Ltd.). The
molding conditions are a mold temperature: 60.degree. C. and a
cylinder temperature: 240.degree. C. In this way, a test piece
composed of a plate-like molded body of 100 mm (width).times.100 mm
(length).times.2 mm (thickness)) was obtained. In addition, an ISO
tensile test piece was obtained by performing the molding in the
same manner. Using these test pieces, the above-described
evaluations were performed, and the results obtained are shown in
Table 4.
Example 2-2
Pellets of the polycarbonate resin composition, obtained in Example
2-1, were uniformly coated with a 15% by weight ethanol solution of
phosphorous acid as the acidic compound (E). Here, the amount of
the acidic compound (E) added was adjusted to become 2 times by mol
relative to the amount of metal (K) in potassium carbonate added as
the compound (C). Thereafter, ethanol was removed by air-drying.
The thus-obtained pellets were melt-extruded in the same manner as
in Example 2-1, thereby performing pelletization. Furthermore,
drying, molding and evaluation of the polycarbonate resin
composition were performed in the same manner as in Example 2-1.
The results obtained are shown in Table 4.
Example 2-3
In this Example, pellets of the polycarbonate resin composition
were manufactured in the same manner as in Example 2-1 except that
15-crown-5-ether was used as the crown ether compound (D), sodium
hydrogencarbonate was used as the compound (C) and the amount of
the compound (C) was changed to 3 ppm by weight in terms of metal
(Na equivalent), and the pellets were uniformly coated with a 15%
by weight ethanol solution of phosphorus acid as the acidic
compound (E). Here, the amount of the acidic compound (E) added was
adjusted to become 2 times by mol relative to the amount of metal
(Na) in sodium hydrogencarbonate added as the compound (C).
Thereafter, ethanol was removed by air-drying. The thus-obtained
pellets were melt-extruded in the same manner as in Example 2-1,
thereby performing pelletization. Furthermore, drying, molding and
evaluation of the polycarbonate resin composition were performed in
the same manner as in Example 2-1. The results obtained are shown
in Table 4.
Example 2-4
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the amount of the
crown ether compound (D) relative to the compound (C) was changed
to 2 times by mol, cesium carbonate was used as the compound (C),
and the amount of the compound (C) was changed to 7 ppm by weight
in terms of metal (Cs equivalent), and a molded body (test piece)
was manufactured using the resin composition and subjected to the
same evaluations as in Example 2-1. The results obtained are shown
in Table 4.
Example 2-5
Pellets of the polycarbonate resin composition, obtained in Example
2-4, were uniformly coated with a 15% by weight ethanol solution of
phosphorus acid as the acidic compound (E). Here, the amount of the
acidic compound (E) added was adjusted to become 2 times by mol
relative to the amount of metal (Cs) in cesium carbonate added as
the compound (C). Thereafter, ethanol was removed by air-drying.
The thus-obtained pellets were melt-extruded in the same manner as
in Example 2-1, thereby performing pelletization. Furthermore,
drying, molding and evaluation of the polycarbonate resin
composition were performed in the same manner as in Example 2-1.
The results obtained are shown in Table 4.
Example 2-6
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the amount of the
crown ether compound (D) relative to the compound (C) was changed
to 0.1 times by mol, lithium carbonate was used as the compound
(C), and the amount of the compound (C) was changed to 10 ppm by
weight in terms of metal (Li equivalent), and a molded body (test
piece) was manufactured using the resin composition and subjected
to the same evaluations as in Example 2-1. The results obtained are
shown in Table 4.
Example 2-7
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the amount of the
crown ether compound (D) relative to the compound (C) was changed
to 0.1 times by mol, lithium stearate was used as the compound (C),
and the amount of the compound (C) was changed to 3 ppm by weight
in terms of metal (Li equivalent), and a molded body (test piece)
was manufactured using the resin composition and subjected to the
same evaluations as in Example 2-1. The results obtained are shown
in Table 4.
Comparative Example 2-1
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the compound (C)
was not added, and a molded body (test piece) was manufactured
using the resin composition and subjected to the same evaluations
as in Example 2-1. The results obtained are shown in Table 5.
Comparative Example 2-2
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the compound (C)
was not added, sodium hydrogencarbonate was used as the crown ether
compound (D), and the amount of the crown ether compound (D) was
changed to 5 ppm by weight in terms of metal (Na equivalent), and a
molded body (test piece) was manufactured using the resin
composition and subjected to the same evaluations as in Example
2-1. The results obtained are shown in Table 5.
Comparative Example 2-3
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the compound (C)
and the crown ether compound (D) were not added, and a molded body
(test piece) was manufactured using the resin composition and
subjected to the same evaluations as in Example 2-1. The results
obtained are shown in Table 5.
Comparative Example 2-4
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that PC-A3 as the
polycarbonate resin (A) was used in place of the aromatic
polycarbonate resin (B) and the compound (C) and the crown ether
compound (D) were not added, and a molded body (test piece) was
manufactured using the resin composition and subjected to the same
evaluations as in Example 2-1. The results obtained are shown in
Table 5.
Reference Example 2-1
This Example was performed in the same manner as in Example 2-1
except that the compound (C) was not added and the amount of
potassium carbonate used as the crown ether compound (D) was
changed to 5 ppm by weight in terms of metal. The results obtained
are shown in Table 5.
Reference Example 2-2
In this Example, a polycarbonate resin composition was manufactured
in the same manner as in Example 2-1 except that the compound (C)
was not added, sodium hydrogencarbonate was used as the crown ether
compound (D), and the amount of the crown ether compound (D) was
changed to 10 ppm by weight in terms of metal (Na equivalent), and
a molded body (test piece) was manufactured using the resin
composition and subjected to the same evaluations as in Example
2-1. The results obtained are shown in Table 5.
TABLE-US-00004 TABLE 4 Example No. Example Example Example Example
Example Example Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 Blending
Polycarbonate PC-A1 parts by weight 70 70 70 70 70 70 70 resin (A)
PC-A3 parts by weight -- -- -- -- -- -- -- Aromatic polycarbonate
parts by weight 30 30 30 30 30 30 30 resin (B) Crown ether kind --
18C6E 18C6E 15C5E 18C6E 18C6E 18C6E 18C6E compound (D) amount times
by mol 1 1 1 2 2 0.1 0.1 added Compound (C) kind -- potassium
potassium sodium cesium cesium lithium lit- hium carbonate
carbonate hydrogen- carbonate carbonate acetate stearate carbonate
amount ppm by weight 2 2 3 7 7 10 3 added Acidic kind -- --
phosphorous phosphorous -- phosphorous -- -- compound acid acid
acid (E) amount times by mol -- 2 2 -- 2 -- -- added Metal amount
(total) ppm by weight 2 2 3 7 7 10 3 Properties Glass transition
singularity -- A A A A A A A temperature Tg .degree. C. 125 125 125
125 125 120 120 (DSC method) Total light transmittance % 88.9 88.7
89.8 87.6 87.7 87.4 87.8 Haze % 0.3 0.3 0.2 0.3 0.1 0.3 0.2 Wet
heat resistance % 0.2 0.1 1.1 0.3 0.1 0.8 0.8 (85.degree. C./85 RH
%) .DELTA.Haze@480 hr High-rate condition of % 100 100 100 100 100
100 100 impact test 23.degree. C. condition of % 80 100 60 80 80 0
0 -20.degree. C. Bending modulus MPa 2800 2800 2800 2750 2800 2800
2800 Heat resistance .degree. C. 104 107 108 108 108 107 107
(DTUL@1.80 MPa) Biogenic substance % 46.5 46.5 46.5 46.5 46.5 46.5
46.5 content rate (C.sup.14 estimation)
TABLE-US-00005 TABLE 5 Comparative Example No. Comparative
Comparative Comparative Comparative Reference Reference Example 2-1
Example 2-2 Example 2-3 Example 2-4 Example 2-1 Example 2-2
Blending Polycarbonate PC-A1 parts by weight 70 70 70 70 70 70
resin (A) PC-A3 parts by weight -- -- -- 30 -- -- Aromatic
polycarbonate parts by weight 30 30 30 -- 30 30 resin (B) Crown
ether kind -- -- -- -- -- -- -- compound (D) amount times by mol --
-- -- -- -- -- added Compound (C) kind -- potassium sodium -- --
potassium sodium carbonate hydrogen- carbonate hydrogen- carbonate
carbonate amount ppm by weight 2 5 -- -- 5 10 added Acidic kind --
-- -- -- -- -- -- compound (E) amount times by mol -- -- -- -- --
-- added Metal amount (total) ppm by weight 2 5 0.4 0.4 5 10
Properties Glass transition singularity -- C C C A A A temperature
Tg .degree. C. 122/136 121/136 122/137 89 125 124 (DSC method)
Total light % opaque opaque opaque 89.7 85.8 89.8 transmittance
Haze % opaque opaque opaque 1.9 1 0.5 Wet heat resistance % -- --
-- 1.7 1.4 93.2 (85.degree. C./85 RH %) .DELTA.Haze@480 hr
High-rate condition of % 0 0 0 100 80 0 impact test 23.degree. C.
condition of % 0 0 0 100 0 0 -20.degree. C. Bending modulus MPa
2750 2700 2750 2200 2800 2650 Heat resistance .degree. C. 108 108
108 75 107 107 (DTUL@1.80 MPa) Biogenic substance % 46.5 46.5 46.5
18 46.5 46.5 content rate (C.sup.14 estimation)
As seen from Tables 4 and 5, the polycarbonate resin composition of
Examples contains a polycarbonate resin (A) containing a
constitutional unit derived from a compound represented by formula
(1), an aromatic polycarbonate resin (B), a crown ether compound
(D), and at least one compound (C) selected from the group
consisting of compounds of Group I metals of the long-form periodic
table and compounds of Group II metals of the long-form periodic
table, in which the content of the compound (C), per 100 parts by
weight of the total amount of the polycarbonate resin (A) and the
aromatic polycarbonate resin (B), is from 0.8 to 1,000 ppm by
weight in terms of metal amount in the compound (C) and the content
of the crown ether compound (D) relative to the compound (C) is
from 0.1 to 10 times by mol. Such a polycarbonate resin composition
had excellent transparency and at the same time, possessed high
levels of biogenic substance content rate, heat resistance, wet
heat resistance and impact resistance in a balanced manner.
While the invention has been described in detail and with reference
to embodiments thereof, it will be apparent to one skilled in the
art that various changes and modifications can be made therein
without departing from the spirit and scope of the invention. This
application is based on Japanese Patent Application (Patent
Application No. 2015-131491) filed on Jun. 30, 2015 and Japanese
Patent Application (Patent Application No. 2015-131492) filed on
Jun. 30, 2015, the entirety of which is incorporated herein by way
of reference. In addition, all the references cited herein are
incorporated by reference in their entirety.
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